Catalytic [2 + 2] and [3 + 2] cycloaddition reactions

Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2012

Catalytic [2 + 2] and [3 + 2] cycloaddition reactions of allenonates with cyclic ketimines Xiang-Yu Chen, Ruo-Chen Lin and Song Ye* Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China [email protected] Table of Contents Part I General Information.............................................................................................2 Part II Experimental part................................................................................................2 1. Materials................................................................................................................................2 2. DABCO-catalyzed [2 + 2] cycloaddition (Table 2). .............................................................3 3. PPh3-catalyzed [3 + 2] cycloaddition (Table 3)...................................................................13 4. PBu3-catalyzed [3 + 2] cycloaddition (Scheme 1). .............................................................22 5. Chiral catalysts for the reactions (Table S1). ......................................................................24 6. Control experiments for expansion of cycloadduct 3j to 4j/5j ............................................24 7. X-Ray structures of cycloadduct 3a and 5a (Fig. S1 and S2)..............................................25 8. References...........................................................................................................................26

Part III NMR Spectra...................................................................................................27

1


Part I General Information Unless otherwise indicated, all reactions were carried out under N2 atmosphere in oven-dried glassware with magnetic stirring. Anhydrous THF and toluene were distilled from sodium and benzophenone. Anhydrous CH2Cl2 was distilled from CaH2. Column chromatograph was performed on silica gel 200~300 mesh. All 1H NMR (300 MHz),

13

C NMR (75 MHz) spectra were recorded on a Bruker-DMX 300

spectrometer in CDCl3, with tetramethylsilane as an internal standard and reported in parts per million (ppm, δ). 1H NMR Spectroscopy splitting patterns were designated as singlet (s), doublet (d), triplet (t). Splitting patterns that could not be interpreted or easily visualized were designated as multiplet (m) or broad (br). Infrared spectra were recorded on a JASCO FT/IR-480 spectrophotometer and reported as wave number (cm-1).

Part II Experimental part

1. Materials Both cyclic ketimines1 and ethyl 2,3-butadienoate2 were prepared according to literature methods.

2


2. DABCO-catalyzed [2 + 2] cycloaddition (Table 2). O O S N

CO2Et

DABCO (20 mol%)

+

O O S N E

toluene, rt, 24-36 h R

R 1

CO2Et

3 (E-isomer only)

2

To a stirred solution of cyclic ketimines (0.2 mmol) and DABCO (4.5 mg, 0.04 mmol) in toluene (2 mL) was added ethyl 2,3-butadienoate (48.8 mg, 0.4 mmol). The reaction mixture was stirred for 24-36 h at room temperature until the full consumption of the cyclic ketimines. The reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (petroleum ether/EtOAc, typically 10:1-5:1) to furnish the corresponding [2+2] cycloadduct 3.

O O S N

CO2Et

Ph 3a

(E)-ethyl

2-(4,4-dioxido-8b-phenyl-1H-azeto[1,2-b]benzo[d]isothiazol-2-(8bH)-

ylidene)acetate Reaction time: 24 h; Yield: 61 mg, 86%; white solid; mp 154 oC; Rf = 0.25 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.77 (d, J = 7.7 Hz, 1H), 7.71-7.51 (m, 4H), 7.49-7.29 (m, 4H), 5.94 (t, J = 2.3 Hz, 1H), 4.11 (q, J = 7.2 Hz, 2H), 4.04 (dd, J = 17.1, 2.3 Hz, 1H), 3.76 (dd, J = 17.1, 2.3 Hz, 1H), 1.23 (t, J = 7.1 Hz, 3H).

13

C NMR (75 MHz, CDCl3): δ 166.1, 155.9, 143.0, 139.1, 136.2,

3


134.2, 130.1, 129.0, 128.6, 125.3, 124.9, 122.1, 104.8, 76.9, 60.1, 43.2, 14.3. IR (KBr): 1713, 1671, 1449, 1336, 1181, 1111, 763, 573, 526. HRMS (EI) calcd for C19H17NO4S [M]+ 355.0878, found 355.0883.

O O S N

CO2Et

3b

(E)-ethyl 2-(4,4-dioxido-8b-(p-tolyl)-1H-azeto[1,2-b]benzo[d]isothiazol-2(8bH)ylidene)acetate Reaction time: 36 h; Yield: 59 mg, 80%; white solid; mp 140 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.77 (d, J = 7.8 Hz, 1H), 7.62 (d, J = 7.6 Hz, 1H), 7.55 (t, J = 7.5 Hz, 1H), 7.44 (t, J = 7.1 Hz, 3H), 7.21 (d, J = 8.0 Hz, 2H), 5.94 (d, J = 2.1 Hz, 1H), 4.11 (q, J = 7.1 Hz, 2H), 4.03 (dd, J = 17.1, 2.1 Hz, 1H), 3.73 (dd, J = 17.1, 2.1 Hz, 1H), 2.34 (s, 3H), 1.23 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 166.2, 156.0, 143.2, 138.6, 136.3, 136.0, 134.2, 130.0, 129.6, 125.3, 124.9, 122.1, 104.7, 76.9, 60.1, 43.0, 21.1, 14.3. IR (KBr): 1713, 1671, 1336, 1182, 1108, 1042, 821, 760, 584, 526. HRMS (EI) calcd for C20H19NO4S [M]+ 369.1035, found 369.1039.

4


O O S N CO2Et

MeO

3c (E)-ethyl 2-(8b-(4-methoxyphenyl)-4,4-dioxido-1H-azeto[1,2-b]benzo[d]isothiazol -2(8bH)-ylidene)acetate Reaction time: 36 h; Yield: 35 mg, 45%; white solid; mp 140 oC; Rf = 0.33 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.79 (d, J = 7.8 Hz, 1H), 7.65-7.56 (m, 2H), 7.47 (d, J = 8.8 Hz, 2H), 7.41 (d, J = 7.7 Hz, 1H), 6.92 (d, J = 8.8 Hz, 2H), 5.93(t, J = 2.4 HZ, 1H), 4.11 (q, J = 7.2 Hz, 2H), 4.04 (dd, J = 17.2, 2.4 Hz, 1H), 3.80 (s, 3H), 3.70 (dd, J = 17.1, 2.3 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 166.3, 159.9, 156.0, 143.4, 136.5, 134.2, 130.9, 130.0, 127.1, 125.0, 122.2, 114.4, 104.7, 76.9, 60.1, 55.4, 43.0, 14.3. IR (KBr): 1713, 1670, 1514, 1336, 1254, 1180, 1108, 833, 530. HRMS (EI) calcd for C20H19NO5S [M]+ 385.0948, found 385.0988. O O S N

CO 2Et

CN

3d

(E)-ethyl 2-(8b-(4-cyanophenyl)-4,4-dioxido-1H-azeto[1,2-b]benzo[d]isothiazol2(8bH)-ylidene)acetate

5


Reaction time: 24 h; Yield: 53 mg, 70%; white solid; mp 146 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.82 (d, J = 7.6 Hz, 1H), 7.78-7.58 (m, 6H), 7.46 (d, J = 7.7 Hz, 1H), 5.96 (t, J = 2.2 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 3.99 (dd, J = 17.0, 2.2 Hz, 1H), 3.81 (dd, J = 17.0, 2.3 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 164.9, 153.8, 143.1, 140.6, 135.3, 133.6, 131.9, 129.6, 125.2, 123.6, 121.5, 117.1, 111.8, 104.3, 74.9, 59.3, 42.2, 13.2. IR (KBr): 2230, 1713, 1672, 1353, 1336, 1182, 1108, 843, 761, 578. HRMS (EI) calcd for C20H16N2O4S [M]+ 380.0831, found 380.0836. O O S N

CO2 Et

Br

3e (E)-ethyl 2-(8b-(4-bromophenyl)-4,4-dioxido-1H-azeto[1,2-b]benzo[d]isothiazol2(8bH)-ylidene)acetate Reaction time: 24 h; Yield: 81 mg, 93%; white solid; mp 140 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.79 (d, J = 7.5 Hz, 1H), 7.67 (dd, J = 10.7, 4.2 Hz, 1H), 7.60 (d, J = 7.6 Hz, 1H), 7.54 (d, J = 8.6 Hz, 2H), 7.49-7.39 (m, 3H), 5.94 (t, J = 2.1 Hz, 1H), 4.11 (q, J = 7.1 Hz,. 2H), 3.99 (dd, J = 17.0, 2.2 Hz, 1H), 3.75 (dd, J = 17.0, 2.2 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H).

13

C

NMR (75 MHz, CDCl3): δ 166.0, 155.4, 142.4, 138.1, 136.3, 134.4, 132.2, 130.3, 127.1, 124.7, 123.0, 122.3, 105.0, 76.3, 60.2, 43.1, 14.3. IR (KBr): 1713, 1675, 1336,

6


1181, 1108, 994, 835, 759, 575. HRMS (EI) calcd for C19H16BrNO4S [M]+ 432.9983, 434.9963, found 432.9987, 434.9970. O O S N

CO 2Et

3f (E)-ethyl 2-(4,4-dioxido-8b-(m-tolyl)-1H-azeto[1,2-b]benzo[d]isothiazol-2(8bH)ylidene)acetate Reaction time: 36 h; Yield: 65 mg, 88%; white solid; mp 189 oC; Rf = 0.33 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.79 (d, J = 7.8 Hz, 1H), 7.65 (td, J = 7.6, 1.1 Hz, 1H), 7.57 (dd, J = 11.2, 3.8 Hz, 1H), 7.45 (d, J = 7.7 Hz, 1H), 7.37-7.30 (m, 3H), 7.16 (d, J = 7.3 Hz, 1H), 5.93 (t, J = 2.3 Hz, 1H), 4.11 (q, J = 7.1 Hz, 2H), 4.03 (dd, J = 17.1, 2.3 Hz, 1H), 3.74 (dd, J = 17.1, 2.4 Hz, 1H), 2.37 (s, 3H), 1.24 (t, J = 7.1 Hz, 3H).

13

C NMR (75 MHz, CDCl3): δ 166.2,

156.0, 143.2, 139.1, 138.9, 136.3, 134.2, 130.1, 129.5, 128.9, 126.0, 124.9, 122.4, 122.2, 104.8, 77.0, 60.1, 43.3, 21.6, 14.3. IR (KBr): 1713, 1671, 1336, 1182, 1112, 1039, 843, 761, 575. HRMS (EI) calcd for C20H19NO4S [M]+ 369.1035, found 369.1040. O O S N

CO 2Et

CN

3g

(E)-ethyl 2-(8b-(3-cyanophenyl)-4,4-dioxido-1H-azeto[1,2-b]benzo[d]isothiazol-

7


2(8bH)-ylidene)acetate Reaction time: 24 h; Yield: 61 mg, 80%; white solid; mp 167 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.90-7.87 (m, 2H), 7.83 (d, J = 7.7 Hz, 1H), 7.77-7.53 (m, 4H), 7.48 (d, J = 7.8 Hz, 1H), 5.96 (t, J = 2.3 Hz, 1H), 4.12 (q, J = 7.1 Hz, 1H), 4.00 (dd, J = 17.0, 2.3 Hz, 1H), 3.81 (dd, J = 17.0, 2.3 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H).

13

C NMR (75 MHz, CDCl3): δ 165.9,

154.80, 141.6, 140.8, 136.3, 134.6, 132.3, 130.6, 130.1, 129.9, 128.86, 124.7, 122.4, 118.1, 113.3, 105.3, 75.5, 60.3, 43.3, 14.2. IR (KBr): 2231, 1713, 1671, 1353, 1333, 1183, 1112, 761, 729. HRMS (EI) calcd for C20H16N2O4S [M]+ 380.0831, found 380.0836. O O S N

CO 2Et

CF3

F3 C

3h

(E)-ethyl 2-(8b-(3,5-bis(trifluoromethyl)phenyl)-4,4-dioxido-1H-azeto [1,2-b]benzo[d]isothiazol-2(8bH)-ylidene)acetate Reaction time: 24 h; Yield: 93 mg, 95%; white solid; mp 136 oC; Rf = 0.33 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.11 (s, 2H), 7.91-7.83 (m, 2H), 7.75 (t, J = 7.3 Hz, 1H), 7.66 (t, J = 7.5 Hz, 1H), 7.51 (d, J = 7.6 Hz, 1H), 5.99 (s, 1H), 4.13 (q, J = 7.1 Hz, 2H), 3.95 (dd, J = 45.2, 17.0 Hz, 1H), 1.25 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 165.8, 154.4, 142.0, 141.1, 136.5, 134.8, 134.0, 132.7 (q, JC-F = 37.5 Hz), 130.9, 125.7, 124.6, 122.9 (q, JC-F = 271.5 Hz),

8


122.6, 105.5, 75.2, 60.4, 43.6, 14.2. IR (KBr): 1714, 1674, 1337, 1280, 1183, 1135, 901, 705, 681, 572. HRMS (EI) calcd for C21H15F6NO4S [M]+ 491.0626, found 491.0633. O O S N

CO 2Et

N

3i

(E)-ethyl 2-(4,4-dioxido-8b-(pyridin-2-yl)-1H-azeto[1,2-b]benzo[d]isothiazol2(8bH)-ylidene)acetate Reaction time: 24 h; Yield: 68 mg, 96%; orange solid; mp 132 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.66 (d, J = 4.8 Hz, 1H), 7.88 (d, J = 7.7 Hz, 1H), 7.81-7.52 (m, 5H), 7.37-7.16 (m, 1H), 5.96 (t, J = 2.1 Hz, 1H), 4.22-4.00 (m, 3H), 3.75 (dd, J = 17.5, 2.2 Hz, 1H), 1.23 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 165.9, 157.7, 156.2, 149.6, 141.6, 137.3, 136.2, 134.2, 130.3, 125.9, 123.2, 121.8, 120.2, 105.0, 76.0, 60.1, 42.9, 14.3. IR (KBr): 1714, 1671, 1448, 1353, 1336, 1182, 1112, 1093, 842, 753, 574, 527. HRMS (EI) calcd for C18H16N2O4S [M]+ 356.0831, found 356.0835.

O O S N CO 2tBu Ph

3j

(E)-tert-butyl 2-(4,4-dioxido-8b-phenyl-1H-azeto[1,2-b]benzo[d]isothiazol2(8bH)-ylidene)acetate 9


Reaction time: 1 d; Yield: 73 mg, 94%; white solid; mp 160 oC; Rf = 0.5 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.77 (d, J = 7.7 Hz, 1H), 7.69-7.50 (m, 4H), 7.49-7.31 (m, 4H), 5.85 (t, J = 2.3 Hz, 1H), 4.01 (dd, J = 17.0, 2.3 Hz, 1H), 3.73 (dd, J = 17.0, 2.3 Hz, 1H), 1.42 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 165.6, 154.8, 143.2, 139.3, 136.3, 134.3, 130.1, 129.1, 128.7, 125.4, 124.9, 122.2, 106.7, 80.6, 77.0, 43.3, 28.3. IR (KBr): 1700, 1670, 1381, 1270, 728, 573. HRMS (EI) calcd for C21H21NO4S [M]+ 383.1191, found 383.1196.

O O S N CO 2Cy Ph

3k

(E)-cyclohexyl 2-(4,4-dioxido-8b-phenyl-1H-azeto[1,2-b]benzo[d] isothiazol-2(8bH)-ylidene)acetate Reaction time: 1 d; Yield: 80 mg, 98%; white solid; mp 130 oC; Rf = 0.5 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.78 (d, J = 7.8 Hz, 1H), 7.68-7.51 (m, 4H), 7.49-7.31 (m, 4H), 5.93 (t, J = 2.3 Hz, 1H), 4.76-4.72 (m, 1H), 4.03 (dd, J = 17.0, 2.3 Hz, 1H), 3.75 (dd, J = 17.0, 2.3 Hz, 1H), 1.90-1.62 (m, 4H), 1.52-1.20 (m, 6H).

13

C NMR (75 MHz, CDCl3): δ 165.7, 155.6, 143.1, 139.2,

136.3, 134.3, 130.2, 129.1, 128.7, 125.4, 124.9, 122.2, 105.5, 76.9, 72.6, 43.4, 31.8, 31.8, 25.4, 23.8. IR (KBr): 1852, 1687, 1351, 1226, 768, 503. HRMS (EI) calcd for C23H23NO4S [M]+ 409.1348, found 409.1352.

10


O O S N CO 2Bn Ph

3l

(E)-benzyl 2-(4,4-dioxido-8b-phenyl-1H-azeto[1,2-b]benzo[d] isothiazol-2(8bH)-ylidene)acetate Reaction time: 1 d; Yield: 76 mg, 91%; white solid; mp 146 oC; Rf = 0.4 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.74 (d, J = 7.8 Hz, 1H), 7.66-7.47 (m, 4H), 7.46-7.35 (m, 4H), 7.36-7.25 (m, 5H), 6.00 (t, J = 2.2 Hz, 1H), 5.09 (s, 2H), 4.02 (dd, J = 17.1, 2.3 Hz, 1H), 3.74 (dd, J = 17.1, 2.3 Hz, 1H).

13

C

NMR (75 MHz, CDCl3): δ 166.0, 156.6, 143.0, 139.1, 136.3, 136.0, 134.3, 130.2, 129.1, 128.7, 128.6, 128.3, 125.4, 124.9, 122.3, 104.4, 76.9, 66.0, 43.3. IR (KBr): 1705, 1670, 1344, 1108, 700, 572, 571. HRMS (EI) calcd for C24H19NO4S [M]+ 417.1035, found 417.1039.

O O S N CO2 tBu

MeO

3m

(E)-tert-butyl 2-(8b-(4-methoxyphenyl)-4,4-dioxido-1H-azeto[1,2-b]benzo [d]isothiazol-2(8bH)-ylidene)acetate Reaction time: 5 d; Yield: 51 mg, 61%; white solid; mp 191 oC; Rf = 0.4 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.79 (d, J = 7.9

11


Hz, 1H), 7.72-7.51 (m, 2H), 7.50-7.36 (m, 3H), 7.02-6.81 (m, 2H), 5.84 (t, J = 2.3 Hz, 1H), 4.01 (dd, J = 17.0, 2.3 Hz, 1H), 3.80 (s, 3H), 3.67 (dd, J = 17.0, 2.3 Hz, 1H), 1.43 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 165.7, 160.0, 155.0, 143.6, 136.6, 134.3, 131.2, 130.1, 127.2, 125.0, 122.3, 114.4, 106.7, 80.6, 77.0, 55.5, 43.0, 28.4. IR (KBr): 1707, 1670, 1343, 1132, 762, 553. HRMS (EI) calcd for C22H23NO5S [M]+ 413.1297, found 413.1303.

O O S N CO 2tBu Ph

3a'

(E)-tert-butyl 2-(7-methyl-4,4-dioxido-8b-phenyl-1H-azeto[1,2-b]benzo[d] isothiazol-2(8bH)-ylidene)acetate Reaction time: 1 d; Yield: 70 mg, 89%; white solid; mp 157 oC; Rf = 0.6 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.65 (d, J = 8.0 Hz, 1H), 7.61-7.55 (m, 2H), 7.47-7.29 (m, 4H), 7.20 (s, 1H), 5.84 (t, J = 2.3 Hz, 1H), 3.99 (dd, J = 17.0, 2.3 Hz, 1H), 3.72 (dd, J = 17.0, 2.3 Hz, 1H), 2.41 (s, 3H), 1.42 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 165.6, 155.1, 145.6, 143.6, 139.5, 133.8, 131.1, 129.0, 128.6, 125.4, 125.0, 121.9, 106.6, 80.5, 76.8, 43.2, 28.3, 21.9. IR (KBr): 1707, 1670, 1343, 1132, 762, 553. HRMS (EI) calcd for C22H23NO4S [M]+ 397.1348, found 397.1353.

12


3. PPh3-catalyzed [3 + 2] cycloaddition (Table 3). O O S N

CO2Et

+

PPh 3 (20 mol%)

O O S N

toluene, rt, 3 d R

R 1

5

2

CO2Et

To a stirred solution of cyclic ketimines (0.2 mmol) and PPh3 (10.5 mg, 0.04 mmol) in toluene (2 mL) was added ethyl 2,3-butadienoate (48.8 mg, 0.4 mmol). The reaction mixture was stirred for 3 d at room temperature until the full consumption of the cyclic ketimines. The reaction mixture was concentrated under reduced pressure, and the

residue

was

purified

by

column

chromatography

on

silica

gel

(petroleumether/EtOAc as the eluent, typically 10:1-5:1) to furnish the corresponding [3+2] cycloadduct 5.

O O S N CO2 Et

5a

ethyl 9b-phenyl-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 75 mg, 75%; white solid; mp 156 oC; Rf = 0.4 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.00 (dd, J = 6.9, 1.6 Hz, 1H), 7.86-7.80 (m, 1H), 7.61 (m, 2H), 7.30 (dt, J = 4.5, 2.4 Hz, 3H), 7.25-7.18 (m, 2H), 7.10 (t, J = 2.2 Hz, 1H), 4.79 (dd, J = 18.4, 2.5 Hz, 1H), 4.26 (dd, J = 15.8, 2.6 Hz, 1H), 4.21 (q, J = 7.1 Hz, 2H), 1.26 (t, J = 7.1 Hz, 3H). 13C NMR (75 13


MHz, CDCl3): δ 162.2, 141.0, 140.8, 140.1, 136.0, 135.8, 133.1, 130.0, 128.6, 128.4, 127.9, 126.8, 121.4, 82.8, 61.3, 52.6, 14.1. IR (KBr): 1717, 1315, 1175, 1315, 1175, 1112, 762, 697, 572. HRMS (EI) calcd for C19H17NO4S [M]+ 355.0878, found 355.0883.

O O S N CO2 Et

5b

ethyl

9b-(p-tolyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-1-carboxylate

5,5-dioxide Reaction time: 3 d; Yield: 40 mg, 54%; white solid; mp 128 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 5:1); 1H NMR (300 MHz, CDCl3): δ 8.01-7.98 (m, 1H), 7.82 (dd, J = 6.8, 1.9 Hz, 1H), 7.68-7.53 (m, 2H), 7.14-7.05 (m, 5H), 4.78 (dd, J = 18.4, 2.5 Hz, 1H), 4.33-4.09 (m, 3H), 2.31 (s, 3H), 1.27 (t, J = 7.1 Hz, 3H).

13

C

NMR (75 MHz, CDCl3): δ 162.2, 140.8, 140.3, 138.3, 138.0, 136.0, 135.8, 133.0, 129.9, 129.3, 127.9, 126.7, 121.3, 82.7, 61.2, 52.5, 21.1, 14.1. IR (KBr): 1716, 1511, 1317, 1175, 1108, 923, 755, 571, 523. HRMS (EI) C20H19NO4S [M]+ 369.1035, found 369.1039.

14


O O S N CO2 Et

NC

5d

ethyl 9b-(4-cyanophenyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b] isothiazole-1carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 56 mg, 74%; white solid; mp 132 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 5:1); 1H NMR (300 MHz, CDCl3): δ 8.00-7.97 (m, 1H), 7.86-7.83 (m, 1H), 7.70-7.59 (m, 4H), 7.39 (d, J = 8.5 Hz, 2H), 7.12 (t, J = 2.0 Hz, 1H), 4.81 (dd, J = 18.5, 2.3 Hz, 1H), 4.35 (dd, J = 18.5, 1.8 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 162.0, 146.0, 141.1, 139.1, 136.1, 135.1, 133.5, 132.3, 130.5, 127.8, 127.5, 121.7, 118.4, 112.3, 81.8, 61.6, 53.7, 14.1. IR (KBr): 2229, 1720, 1450, 1243, 1177, 1112, 926, 765, 574. HRMS (EI) calcd for C20H16N2O4S [M]+ 380.0831, found 380.0835. O O S N CO2 Et

Br

5e

ethyl 9b-(4-bromophenyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 65 mg, 75%; white solid; mp 93 oC; Rf = 0.4 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.00-7.97 (m,

15


1H), 7.83-7.78 (m, 1H), 7.62 (pd, J = 7.3, 1.2 Hz, 2H), 7.44-7.36 (m, 2H), 7.13-7.08 (m, 3H), 4.77 (dd, J = 18.4, 2.4 Hz, 1H), 4.28 (dd, J = 18.4, 1.9 Hz, 1H), 4.21 (q, J = 7.2 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 162.0, 140.9, 140.0, 139.7, 136.0, 135.4, 133.3, 131.6, 130.2, 128.6, 127.6, 122.7, 121.5, 82.1, 61.4, 53.1, 14.1. IR (KBr): 1717, 1325, 1175, 1114, 923, 758, 572. HRMS (EI) calcd for C19H16BrNO4S [M]+ 432.9983, 432.9963, found 432.9987, 432.9969.

O O S N CO2 Et

5f

ethyl 9b-(m-tolyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 49 mg, 66%; white solid; mp 180 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.00–7.95 (m, 1H), 7.87–7.79 (m, 1H), 7.61 (pd, J = 7.3, 1.4 Hz, 2H), 7.24–7.15 (m, 1H), 7.10 (dd, J = 4.3, 2.0 Hz, 2H), 7.04–6.93 (m, 2H), 4.78 (dd, J = 18.4, 2.5 Hz, 1H), 4.32–4.23 (m, 1H), 4.23–4.12 (m, 2H), 2.29 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 162.2, 140.9, 140.7, 140.1, 138.2, 135.9, 133.0, 129.9, 129.3, 128.4, 128.0, 127.4, 123.9, 121.3, 82.8, 61.2, 52.5, 21.6, 14.1. IR (KBr): 1716, 1522, 1316, 1176, 1111, 925, 760, 572. HRMS (EI) calcd for C20H19NO4S [M]+ 369.1035, found 369.1040.

16


O O S N CO2 Et CN

5g

ethyl 9b-(3-cyanophenyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b] isothiazole -1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 59 mg, 77%; white solid; mp 137 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.00-7.97 (m, 1H), 7.90-7.81 (m, 1H), 7.76-7.55 (m, 4H), 7.53-7.38 (m, 2H), 7.12 (t, J = 2.0 Hz, 1H), 4.80 (dd, J = 18.5, 2.3 Hz, 1H), 4.36 (dd, J = 18.5, 1.8 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 1.28 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 161.9, 142.6, 141.1, 139.1, 136.2, 135.1, 133.6, 132.0, 131.4, 130.7, 130.5, 129.4, 127.4, 121.8, 118.6, 112.7, 81.56, 61.6, 53.7, 14.1. IR (KBr): 2230, 1716, 1330, 1176, 1025, 797, 644, 570. HRMS (EI) C20H16N2O4S [M]+ 380.0831, found 380.0835. O O S N

CO 2Et F3 C CF3

5h

ethyl 9b-(3,5-bis(trifluoromethyl)phenyl)-3,9b-dihydrobenzo[d]pyrrolo [1,2-b]isothiazole-1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 61 mg, 62%; white solid; mp 126 oC; Rf = 0.5 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.03 (d, J = 7.5 Hz, 1H), 7.85 (dd, J = 8.0, 7.3 Hz, 2H), 7.77 (s, 2H), 7.75–7.62 (m, 2H), 7.14 (s, 1H), 17


4.82 (dd, J = 18.5, 2.2 Hz, 1H), 4.43 (dd, J = 18.5, 1.5 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 1.26 (t, J = 7.1 Hz, 3H).

13

C NMR (75 MHz, CDCl3): δ 161.9, 143.7, 141.3,

138.8, 136.2, 135.1, 133.7, 131.8 (q, JC-F = 33.1 Hz), 130.7, 127.3, 127.2, 124.9 (q, JC-F = 270 Hz), 122.0, 121.3, 81.3, 61.7, 54.0, 14.0. IR (KBr): 1720, 1372, 1279, 1175, 1134, 841, 763, 569. HRMS (EI) calcd for C21H15F6NO4S [M]+ 491.0626, found 491.0632. O O S N CO Et N 2

5i

ethyl 9b-(pyridin-2-yl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole1-carboxylate 5,5-dioxide Reaction time: 3 d; Yield: 56 mg, 79%; yellow solid; mp 195 oC; Rf = 0.2 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.56 (d, J = 4.1 Hz, 1H), 8.05 (dd, J = 6.5, 2.1 Hz, 1H), 7.84 (dd, J = 6.3, 2.4 Hz, 1H), 7.69-7.53 (m, 3H), 7.25-7.16 (m, 1H), 7.09-7.01 (m, 2H), 4.84 (dd, J = 18.1, 2.4 Hz, 1H), 4.32 (dd, J = 18.0, 1.8 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 162.3, 159.5, 149.0, 139.5, 139.5, 137.1, 135.9, 135.7, 133.2, 130.1, 128.0, 123.2, 121.3, 121.2, 83.8, 61.1, 53.5, 14.1. IR (KBr): 1714, 1671, 1448, 1353, 1336, 1182, 1112, 1093, 842, 753, 574, 527. HRMS (EI) calcd for C18H16N2O4S [M]+ 355.0753, found 355.0757.

18


O O S N Ph

CO2 tBu

5j

tert-butyl 9b-phenyl-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-1carboxylate 5,5-dioxide Reaction time: 2 d; Yield: 56 mg, 73%; yellow solid; mp 158 oC; Rf = 0.6 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.98 (d, J = 7.7 Hz, 1H), 7.82 (d, J = 7.2 Hz, 1H), 7.60 (dq, J = 14.3, 7.1 Hz, 2H), 7.44-7.25 (m, 3H), 7.22-7.12 (m, 2H), 6.98 (s, 1H), 4.73 (dd, J = 18.2, 2.3 Hz, 1H), 4.24 (dd, J = 18.2, 1.4 Hz, 1H), 1.42 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 161.5, 141.2, 140.5, 140.0, 137.1, 136.2, 133.1, 130.0, 128.5, 128.3, 127.7, 126.8, 121.4, 82.7, 82.4, 52.9, 28.1. IR (KBr): 1712, 1310, 1175, 764, 611. HRMS (EI) calcd for C21H21NO4S [M]+ 383.1191, found 383.1195.

O O S N Ph

CO2 Cy

5k cyclohexyl 9b-phenyl-3,9b-dihydrobenzo[d]pyrrolo[1,2-b] isothiazole-1-carboxylate 5,5-dioxide Reaction time: 2 d; Yield: 59 mg, 72%; yellow solid; mp 140 oC; Rf = 0.5 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.00 (dd, J = 6.9, 1.4 Hz, 1H), 7.83 (dd, J = 6.8, 1.9 Hz, 1H), 7.65-7.55 (m, 2H), 7.38-7.27 (m, 3H),

19


7.22-7.19 (m, 2H), 7.09 (t, J = 2.1 Hz, 1H), 4.97-4.66 (m, 2H), 4.27 (dd, J = 18.3, 1.8 Hz, 1H), 1.95-1.62 (m, 4H), 1.58-1.11 (m, 6H). 13C NMR (75 MHz, CDCl3): δ 161.7, 141.1, 140.8, 140.3, 136.3, 136.1, 133.1, 130.0, 128.6, 128.5, 127.9, 126.9, 121.5, 82.8, 74.0, 52.8, 31.6, 31.5, 25.3, 23.8, 23.7. IR (KBr): 1713, 1318, 1240, 1176, 761, 611. HRMS (EI) calcd for C23H23NO4S [M]+ 409.1348, found 409.1354.

O O S N Ph

CO2 Bn

5l

benzyl

9b-phenyl-3,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-1-carboxylate

5,5-dioxide Reaction time: 2 d; Yield: 63 mg, 76%; yellow solid; mp 143 oC; Rf = 0.7 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.93 (dd, J = 6.1, 2.8 Hz, 1H), 7.84-7.76 (m, 1H), 7.56 (dd, J = 5.8, 3.2 Hz, 2H), 7.39-7.17 (m, 10H), 7.13 (t, J = 2.1 Hz, 1H), 5.17 (s, 2H), 4.77 (dd, J = 18.5, 2.5 Hz, 1H), 4.24 (dd, J = 18.5, 1.8 Hz, 1H).

13

C NMR (75 MHz, CDCl3): δ 162.0, 141.7, 140.8, 140.0,

136.1, 135.6, 135.2, 133.2, 130.1, 128.7, 128.7, 128.6, 128.5, 128.3, 127.9, 126.9, 121.4, 82.8, 67.0, 52.8. IR (KBr): 1716, 1315, 1175, 752, 697. HRMS (EI) calcd for C24H19NO4S [M]+ 417.1035, found 417.1040.

20


O O S N CO2 tBu

MeO

5m

tert-butyl 9b-(4-methoxyphenyl)-3,9b-dihydrobenzo[d]pyrrolo[1,2-b] isothiazole-1-carboxylate 5,5-dioxide Reaction time: 5 d; Yield: 56 mg, 67%; yellow solid; mp 155 oC; Rf = 0.5 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 8.05-7.93 (m, 1H), 7.89-7.80 (m, 1H), 7.71-7.52 (m, 2H), 7.19-7.06 (m, 2H), 6.96 (t, J = 2.1 Hz, 1H), 6.89-6.71 (m, 2H), 4.72 (dd, J = 18.1, 2.4 Hz, 1H), 4.24 (dd, J = 18.2, 1.8 Hz, 1H), 3.77 (s, 3H), 1.44 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 161.6, 159.6, 140.9, 139.9, 137.2, 136.3, 133.5, 133.1, 129.9, 128.2, 127.8, 121.5, 113.9, 82.6, 82.4, 55.4, 52.7, 28.2. IR (KBr): 1713, 1253, 1174, 756, 612. HRMS (EI) calcd for C22H23NO5S [M]+ 413.1297, found 413.1302.

O O S N Ph

CO 2tBu

5a'

tert-butyl 8-methyl-9b-phenyl-3,9b-dihydrobenzo[d]pyrrolo[1,2-b] isothiazole-1-carboxylate 5,5-dioxide Reaction time: 2 d; Yield: 63 mg, 80%; white solid; mp 163 oC; Rf = 0.6 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.76 (s, 1H), 7.70 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.34-7.24 (m, 3H), 7.22-7.13 (m, 21


2H), 6.98 (t, J = 1.9 Hz, 1H), 4.72 (dd, J = 18.2, 2.4 Hz, 1H), 4.23 (dd, J = 18.2, 1.7 Hz, 1H), 2.43 (s, 3H), 1.42 (s, 9H).

13

C NMR (75 MHz, CDCl3): δ 161.6, 144.1,

141.4, 140.9, 140.0, 137.2, 133.7, 130.9, 128.5, 128.3, 127.8, 126.9, 121.2, 82.6, 82.3, 52.9, 28.1, 22.0. IR (KBr): 1709, 1308, 1105, 834, 604. HRMS (EI) calcd for C22H23NO4S [M]+ 397.1348, found 397.1353.

4. PBu3-catalyzed [3 + 2] cycloaddition (Scheme 1). O O S N

+

CO2Et

PBu3 (20 mol%)

O O S N

toluene, rt, 3 d

R 1

CO 2 Et

R 4

2

To a stirred solution of cyclic ketimines (0.2 mmol) and PBu3 (8.1 mg, 0.04 mmol) in toluene (2 mL) was added ethyl 2,3-butadienoate (48.8 mg, 0.4 mmol). The reaction mixture was stirred for 3 d at room temperature until the full consumption of the cyclic ketimines. The reaction mixture was concentrated under reduced pressure, and the

residue

was

purified

by

column

chromatography

on

silica

gel

(petroleumether/EtOAc, typically 20:1-5:1) to furnish the corresponding [3+2] cycloadduct 4. O O S N

4a

22

CO2Et


ethyl 9b-phenyl-1,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-3-carboxylate 5,5-dioxide Reaction time: 3 d; 3a:4a:5a = 9:82:9. Yield of pure 4a: 37 mg, 52%; white solid; mp 165 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 3:1); 1H NMR (300 MHz, CDCl3): δ 7.74 (d, J = 7.8 Hz, 1H), 7.69 (dd, J = 5.5, 3.6 Hz, 2H), 7.61 (td, J = 7.6, 1.2 Hz, 1H), 7.54-7.43 (m, 2H), 7.42-7.35 (m, 2H), 7.34-7.27 (m, 1H), 6.34 (dd, J = 3.2, 2.7 Hz, 1H), 4.47-4.27 (m, 2H), 3.56 (ddd, J = 20.9, 18.3, 3.0 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H).

13

C NMR (75 MHz, CDCl3): δ 160.7, 143.4, 142.4, 136.2, 134.5,

134.0, 129.9, 129.0, 128.4, 125.5, 124.4, 124.2, 122.5, 79.1, 61.8, 46.0, 14.1. IR (KBr): 1729, 1330, 1178, 739, 571. HRMS (EI) calcd for C19H17NO4S [M]+ 355.0878, found 355.0882. O O S N

CO2 Et

4f

ethyl 9b-(m-tolyl)-1,9b-dihydrobenzo[d]pyrrolo[1,2-b]isothiazole-3-carboxylate 5,5-dioxide Reaction time: 3 d; 3f:4f:5f = 3:88:9. Yield of 4f: 43 mg, 58%; white solid; mp 148 oC; Rf = 0.3 (petroleum ether/ethyl acetate = 10:1); 1H NMR (300 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.60 (dd, J = 11.0, 4.0 Hz, 1H), 7.55-7.41 (m, 4H), 7.26 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 7.5 Hz, 1H), 6.34 (t, J = 2.8 Hz, 1H), 4.51-4.25 (m, 2H), 3.54 (ddd, J = 20.8, 18.4, 2.9 Hz, 2H), 2.35 (s, 3H), 1.38 (t, J = 7.1 Hz, 3H).

13

C

NMR (75 MHz, CDCl3): δ 160.7, 143.3, 142.4, 138.8, 136.1, 134.4, 134.0, 129.8, 23


129.2, 128.9, 126.1, 124.4, 124.4, 122.5, 122.4, 79.1, 61.7, 46.0, 21.7, 14.1. IR (KBr): 1729, 1634, 1605, 1449, 1371, 1179, 1137, 759, 652, 569. HRMS (EI) calcd for C20H19NO4S [M]+ 369.1035, found 369.1039.

5. Chiral catalysts for the reactions (Table S1). chiral cat. (20 %) 1a

+

3j

2b

+

4j

+

5j

toluene, rt

N

N OBz

H O

N OBn

H O

N

H O

N

OBn

H HO

N

N

6c, trace

6b, trace

6a, trace

N OTMS

6d, trace

H

PPh 2 PPh 2

P

P O

H P tBu

P tBu

O

7c (R)-BINAP

7b (+)-Tangphos

7a (+)-DIOP 5j, 68% yielda, 0% eeb (3j:4j:5j = 0:9:91)c

5j, 45% yielda , 0% eeb (3j:4j:5j = 0:37:63)c

5j, 14% yielda , 0% eeb (3j:4j:5j = 0:0:100)c

a

Isolated yield of pure 5j. by chiral HPLC for 5j. c Determined by the 1H NMR (300 MHz) of the reaction mixture. bDetermined

6. Control experiments for expansion of cycloadduct 3j to 4j/5j O O S N

conditions CO2tBu

Ph

3j

O O S N X

(no reaction)

O O S N

CO2tBu or

Ph

Ph

4j

5j

CO2tBu

conditions A: toluene, rt, 3d, no reaction detected conditions B: DABCO (20 mol%), toluene, rt, 3d, no reaction detected conditions C: PPh3 (20 mol%), toluene, rt, 3d, no reaction detected 24


7. X-Ray structures of cycloadduct 3a and 5a (Fig. S1 and S2) The crystal suitable for X-ray analysis was prepared by slow evaporation of the solvent of the solution of 3a and 5a in chloroform at room temperature (Figure S1 and S2).

O O S N

CO2Et

Ph 3a

Fig. S1 X-ray structures of cycloaddition products 3a

O O S N CO2 Et

5a

Fig. S2 X-ray structures of cycloaddition products 5a.

25


8. References 1.

F. A. Davis, J. C. Towson, D. B. Vashi, R. ThimmaReddy, J. P. McCauley, M. E. Harakal and D. J. Gosciniak, J. Org. Chem., 1990, 55, 1254;

2.

(a) Y.-L. Shi and M. Shi, Org. Lett., 2005, 7, 3057; (b) G. S. Creech and O. Kwon, Org. Lett., 2008, 10, 429;

26


Part III NMR Spectra O O S N

CO 2Et

Ph

3a 7.787 7.761 7.659 7.637 7.634 7.612 7.608 7.602 7.597 7.591 7.573 7.551 7.548 7.526 7.524 7.463 7.437 7.425 7.408 7.403 7.383 7.364 7.360 7.345 7.337 7.259 5.948 5.940 5.932 4.144 4.120 4.097 4.073 4.069 4.061 4.011 4.004 3.788 3.780 3.731 3.724 1.255 1.231 1.208

Current Data Parameters NAME cxy-352-4.19 EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110419 Time 18.54 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zg30 TD 65536 SOLVENT CDCl3 NS 16 DS 0 SWH 8992.806 Hz FIDRES 0.137219 Hz AQ 3.6438515 sec RG 128 DW 55.600 usec DE 8.00 usec TE 299.3 K D1 1.00000000 sec TD0 1

F2 - Processing parameters SI 32768 SF 300.1300060 MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC 1.00

3.07

2.10 1.09 1.06 77.49 77.06 76.88 76.64

2

1

ppm 14.25

3

43.17

4

60.09

5 104.77

6 142.98 139.08 136.24 134.24 130.08 128.98 128.64 125.29 124.85 122.12

155.87

7

166.11

8

1.00

1.01 4.28 4.22

======== CHANNEL f1 ======== NUC1 1H P1 10.80 usec PL1 3.00 dB SFO1 300.1324010 MHz

Current Data Parameters NAME cxy-352-4.19 EXPNO 11 PROCNO 1 F2 - Acquisition Parameters Date_ 20110419 Time 18.57 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 48 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 2048 DW 27.800 usec DE 6.50 usec TE 299.4 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677507 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

170

160

150

140

130

120

110

100

90

80

70

27

60

50

40

30

20

ppm


O O S N CO2 Et

3.5

2.5

0.083 0.001

1.255 1.232 1.208

3.23

2.336

3.12 3.0

2.0

1.5

cxy-366-2 10 1 20110328 18.43 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 6 0 8992.806 0.137219 3.6438515 128 55.600 8.00 296.7 1.00000000 1

1.0

0.5

Hz Hz sec usec usec K sec

ppm

14.25

4.0

21.10

4.5

43.04

5.0

NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 TD0

======== CHANNEL f1 ======== NUC1 1H P1 10.80 usec PL1 3.00 dB SFO1 300.1324010 MHz SI 32768 SF 300.1292021 MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC 1.00

60.07

5.5

77.48 77.06 76.92 76.64

6.0

2.04 1.03 1.06

4.143 4.119 4.095 4.072 4.059 4.052 4.002 3.995 3.757 3.750 3.700 3.693

5.938

6.5

104.66

7.0

143.21 138.64 136.27 136.04 134.19 129.99 129.61 125.33 124.86 122.07

7.5

156.03

8.0

166.16

8.5

1.00

1.08 1.10 1.16 3.16 2.12

7.781 7.755 7.656 7.631 7.606 7.570 7.545 7.520 7.466 7.440 7.419 7.258 7.218 7.191

3b

NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 D11 TD0

cxy-366-2 11 1 20110328 18.46 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 60 4 17985.611 0.274439 1.8219508 574.7 27.800 6.50 296.9 2.00000000 0.03000000 1

Hz Hz sec usec usec K sec sec

======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz SI 32768 SF 75.4675491 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

170

160

150

140

130

120

110

100

90

80

28

70

60

50

40

30

20 ppm


O O S N CO2Et

3c

7.801 7.776 7.774 7.649 7.646 7.624 7.620 7.591 7.587 7.565 7.562 7.540 7.481 7.474 7.459 7.452 7.424 7.399 7.260 6.933 6.926 6.910 6.903 5.936 5.929 5.921 4.146 4.122 4.099 4.075 4.069 4.061 4.011 4.004 3.797 3.731 3.723 3.674 3.666 1.260 1.237 1.213 0.071 -0.001

MeO


3.25 2.5

2.0

1.5

1.0

0.5

ppm

14.30

3.0

42.98

3.5

60.13

4.0

77.48 77.06 76.90 76.64

4.5

104.73

5.0

114.38

5.5

136.52 134.18 130.94 130.02 127.06 124.95 122.17

6.0


55.41

2.29 1.24 3.27 1.11

1.00 6.5

143.44

2.34 7.0

166.28

7.5

159.91 156.02

1.09 2.34 2.24 1.07



cxy-359-429 10 1 20110429 17.04 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 651 4 17985.611 0.274439 1.8219508 812.7 27.800 6.50 300.5 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

29

70

60

50

40

30

20

ppm


O O S N

CO 2Et

CN

0.076 0.000

1.264 1.240 1.217

3.37 3.5

3.0

2.5

2.0

1.5

1.0

0.5

cxy-355-6.10 10 1 20110610 16.28 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 13 0 8992.806 0.137219 3.6438515 228.1 55.600 8.00 299.7 1.00000000 1


ppm 13.24

4.0



42.24

4.5

59.28

5.0

76.48 76.06 75.64 74.87

5.5

104.26

6.0

2.12 1.07 1.07

4.153 4.129 4.105 4.081 4.022 4.014 3.965 3.958 3.842 3.835 3.786 3.778

5.968 5.961 5.954

6.5

111.78

7.0

143.12 140.58 135.33 133.56 131.87 129.64 125.16 123.60 121.49 117.08

7.5 153.78

164.92

8.0

1.00

1.08 6.02 1.07

7.836 7.810 7.771 7.742 7.733 7.700 7.674 7.646 7.621 7.596 7.469 7.444 7.269

3d

Current Data Parameters NAME cxy-355-c EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110613 Time 8.14 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 62 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 1625.5 DW 27.800 usec DE 6.50 usec TE 299.8 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4678238 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

160

150

140

130

120

110

100

90

80

70

30

60

50

40

30

20

ppm


O O S N

CO2 Et

Br 0.079 0.000

1.260 1.236 1.212




1

14.25

ppm

43.08

2

77.48 77.06 76.64 76.25

3

60.18

4

104.96

5


3.38

2.15 1.09 1.08

4.147 4.123 4.100 4.076 4.019 4.012 3.963 3.955 3.783 3.776 3.726 3.719

5.949 5.941 5.934

6

142.40 138.14 136.26 134.37 132.16 130.31 127.12 124.72 122.97 122.26

7

155.38

8

166.04

9

1.00

1.08 1.10 0.99 2.22 3.20

7.806 7.781 7.668 7.643 7.610 7.608 7.585 7.553 7.524 7.478 7.448 7.417 7.266

3e

Current Data Parameters NAME cxy-353-2 EXPNO 11 PROCNO 1 F2 - Acquisition Parameters Date_ 20110402 Time 16.15 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 43 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 512 DW 27.800 usec DE 6.50 usec TE 296.7 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677498 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

170

160

150

140

130

120

110

100

90

80

31

70

60

50

40

30

20

ppm


O O S N

CO2 Et

0.001

1.261 1.237 1.214

2.371

4.146 4.123 4.099 4.075 4.063 4.055 4.006 3.998 3.767 3.760 3.710 3.703

7.801 7.776 7.668 7.646 7.621 7.585 7.561 7.537 7.464 7.439 7.390 7.348 7.320 7.295 7.269 7.260 7.167 7.143 5.939 5.932 5.925

3f NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 TD0

cxy-366-6.16 10 1 20110616 16.00 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 4 0 8992.806 0.137219 3.6438515 256 55.600 8.00 299.6 1.00000000 1


5.0

4.5

4.0

3.0

2.5

3.06

3.25 3.5

2.0

1.5

1.0

0.5 ppm NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 D11 TD0

14.29

5.5

21.58

6.0

2.16 1.15 1.09

1.00 6.5

43.26

7.0

60.13

7.5

77.48 77.06 77.00 76.64

8.0

143.14 139.07 138.91 136.33 134.21 130.06 129.46 128.91 125.96 124.90 122.42 122.19

156.01

166.23

8.5

104.78

1.03 1.11 1.09 1.04 3.21 1.07


cxy-366-6.17 10 1 20110617 16.42 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 304 4 17985.611 0.274439 1.8219508 512 27.800 6.50 299.7 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

32

60

50

40

30

20

ppm


O O S N

CO2 Et

CN

7.901 7.896 7.890 7.882 7.879 7.842 7.816 7.749 7.746 7.724 7.722 7.699 7.696 7.678 7.657 7.652 7.635 7.611 7.587 7.577 7.559 7.532 7.496 7.470 7.275 5.969 5.961 5.954 4.155 4.132 4.108 4.084 4.027 4.019 3.970 3.963 3.840 3.833 3.784 3.776 1.267 1.244 1.220 -0.001

3g Current Data Parameters NAME cxy-367-3.3 EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110303 Time 16.05 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zg30 TD 65536 SOLVENT CDCl3 NS 14 DS 0 SWH 8992.806 Hz FIDRES 0.137219 Hz AQ 3.6438515 sec RG 128 DW 55.600 usec DE 8.00 usec TE 296.1 K D1 1.00000000 sec TD0 1

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm


14.23

4.0

43.27

4.5

60.26

5.0


3.16

2.11 1.04 1.05 5.5

77.48 77.06 76.64 75.48

6.0

105.26

6.5

141.57 140.77 136.34 134.59 132.33 130.63 130.05 129.88 128.86 124.66 122.44 118.06 113.27

7.0

154.80

7.5

165.86

8.0

1.00

2.05 1.07 4.30 1.07


cxy-367-3.4-c 10 1 20110304 16.16 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 52 4 17985.611 0.274439 1.8219508 13004 27.800 8.00 295.9 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

33

70

60

50

40

30

20

ppm


O O S N

CF3

0.091 0.004

1.275 1.252 1.228

3h

4.167 4.143 4.120 4.096 4.056 4.049 3.999 3.992 3.904 3.897 3.848 3.841

5.991

8.105 7.897 7.863 7.837 7.774 7.750 7.725 7.685 7.660 7.635 7.519 7.493 7.274

F3 C

CO2Et




6.5

6.0

5.0

4.5

4.0

3.27

2.10 1.05 1.09 5.5

3.5

3.0

2.5

2.0

1.5

1.0

0.5 ppm


14.23

7.0

43.55

7.5

60.35

8.0

77.48 77.06 76.64 75.19

8.5

165.84 154.41 142.00 141.09 136.53 134.75 134.04 133.42 133.32 132.87 132.43 131.98 130.87 128.34 125.70 124.72 124.57 123.36 122.83 122.78 122.74 122.64 121.87 121.10 117.48 105.50

9.0

1.00

2.05 2.09 1.25 1.10 1.07


cxy-360-6-13-c 10 1 20110614 8.16 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 276 4 17985.611 0.274439 1.8219508 574.7 27.800 6.50 300.0 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

34

70

60

50

40

30

20

ppm


O O S N

CO 2Et

N

0.083 -0.000

1.253 1.229 1.205 14.25

42.88

60.10

77.49 77.06 76.64 76.00

105.03

141.58 137.25 136.22 134.22 130.25 125.86 123.21 121.77 120.15

149.60

157.65 156.15


ppm

Current Data Parameters NAME cxy-365-2 EXPNO 12 PROCNO 1 F2 - Acquisition Parameters Date_ 20110406 Time 18.58 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 37 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 512 DW 27.800 usec DE 6.50 usec TE 297.8 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677500 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

170

160

150

140

130

120

110

100

90

80

70

35

60

50

40

30

20



9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

165.90


3.24

1.06

3.20

4.143 4.120 4.096 4.072 4.063 4.056 3.786 3.778 3.728 3.720

1.00

1.11

1.05 5.31

1.03

8.672 8.656 7.893 7.867 7.782 7.755 7.724 7.695 7.664 7.638 7.599 7.574 7.549 7.277 7.261 7.255 7.244 7.239 5.970 5.963 5.956

3i

10 ppm


O O S N CO 2tBu Ph

4.5

4.0

3.5

0.082 0.000

1.423

3.0

2.5

2.0

1.5

1.0

0.5

cxy-652 10 1 20111103 20.59 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 16 0 8992.806 0.137219 3.6438515 71.8 55.600 8.00 297.9 1.00000000 1


ppm


28.28

5.0

43.26

5.5

9.25

1.03 1.06

4.044 4.037 3.988 3.980 3.761 3.753 3.704 3.696

5.862 5.854 5.847

6.0



80.60 77.59 77.16 77.01 76.74

6.5

106.71

7.0

143.16 139.30 136.34 134.31 130.14 129.05 128.69 125.39 124.93 122.22

7.5

154.84

8.0

165.55

8.5

1.00

1.03 4.17 4.18

7.785 7.759 7.630 7.606 7.604 7.594 7.590 7.567 7.544 7.520 7.456 7.430 7.402 7.376 7.353 7.330 7.254

3j

cxy-652 11 1 20111103 21.04 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 28 4 17985.611 0.274439 1.8219508 812.7 27.800 6.50 298.0 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

36

70

60

50

40

30

ppm


O O S N CO 2Cy Ph

1.798 1.697 1.677 1.528 1.516 1.497 1.408 1.370 1.359 1.347 1.338 1.306 1.300 1.271 0.082 0.000

1

cxy-668-a 10 1 20111117 16.35 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 12 0 8992.806 0.137219 3.6438515 64 55.600 8.00 296.5 1.00000000 1


ppm


25.41 23.80

31.79 31.75

2

77.59 77.16 76.94 76.74 72.55

3

6.27

4.02

4



43.35

5

1.05 1.05

1.09

6

105.45

7

143.08 139.22 136.32 134.32 130.16 129.06 128.70 125.37 124.94 122.21

8

155.58

165.66

9

1.00

1.05 4.26 4.28

7.788 7.762 7.658 7.637 7.634 7.612 7.604 7.599 7.575 7.549 7.547 7.525 7.522 7.469 7.443 7.436 7.430 7.424 7.407 7.382 7.358 7.343 7.335 7.259 5.935 5.928 5.920 4.761 4.747 4.732 4.719 4.058 4.050 4.001 3.993 3.780 3.773 3.724 3.716

3k

cxy-668-a 11 1 20111117 16.38 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 31 4 17985.611 0.274439 1.8219508 322.5 27.800 6.50 296.9 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

37

60

50

40

30

ppm


O O S N CO 2Bn Ph

0.091 0.000

4.048 4.041 3.991 3.984 3.775 3.767 3.717 3.710

1.07 1.07 4

3

1

77.59 77.16 76.95 76.74

2



0 ppm


43.28

5

66.03

2.10

6



104.43

7

142.96 139.09 136.30 135.99 134.33 130.18 129.06 128.74 128.60 128.25 125.35 124.93 122.19

156.60

8

165.98

9

1.00

1.12 4.19 4.02 5.18

7.757 7.731 7.624 7.603 7.599 7.577 7.573 7.549 7.539 7.517 7.514 7.492 7.489 7.412 7.401 7.388 7.383 7.363 7.347 7.342 7.338 7.319 7.309 7.301 7.296 7.224 6.003 5.995 5.988 5.092

3l




170

160

150

140

130

120

110

100

90

80

38

70

60

50

40

ppm


O O S N CO2 tBu

MeO

0.072 0.000

1.427

cxy-663-a 10 1 20111110 16.25 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 7 0 8992.806 0.137219 3.6438515 256 55.600 8.00 298.5 1.00000000 1


ppm


28.35

43.04

55.50

80.62 77.58 77.16 77.03 76.74

106.67

114.44

136.61 134.25 131.16 130.08 127.16 125.03 122.26

143.62

154.97

159.95

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

165.72



9.12

4.047 4.039 3.990 3.982 3.796 3.705 3.698 3.649 3.641

1.06 3.18 1.10

1.00

2.15

1.06 2.16 3.17

7.803 7.777 7.648 7.645 7.623 7.619 7.591 7.587 7.565 7.562 7.540 7.476 7.469 7.453 7.446 7.436 7.419 7.394 7.261 6.928 6.922 6.906 6.899 5.850 5.842 5.835

3m

cxy-663-a 11 1 20111110 16.27 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 118 4 17985.611 0.274439 1.8219508 322.5 27.800 6.50 298.7 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

39

60

50

40

30

20

ppm


O O S N CO 2tBu Ph

0.081 -0.000

1.422

9.28



0 ppm

28.28

1

80.52 77.58 77.16 76.79 76.74

2


21.91

2.408

3



43.15

4

106.55

5

3.14

1.06 1.07

4.024 4.016 3.968 3.960 3.751 3.744 3.695 3.687

5.846 5.839 5.831

6

145.56 143.58 139.50 133.75 131.13 129.02 128.60 125.41 125.00 121.92

7

155.07

165.60

8

1.00

1.06 2.08 4.10 1.13

7.659 7.632 7.598 7.593 7.569 7.429 7.406 7.381 7.355 7.331 7.257 7.200

3a'




170

160

150

140

130

120

110

100

90

80

70

40

60

50

40

30

ppm


O O S N

CO2 Et

6.5

6.0

5.5

5.0

3.07

1.11 2.28 4.5

4.0

3.0

2.5

82.75 77.48 77.06 76.64

3.5

2.0

1.5

1.0

0.5

cxy-349 10 1 20110224 16.23 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 16 0 8992.806 0.137219 3.6438515 256 55.600 8.00 296.7 1.00000000 1


ppm 14.10

7.0



52.62

7.5

61.25

8.0

140.99 140.83 140.05 135.92 135.79 133.11 129.96 128.55 128.43 127.94 126.77 121.36

162.15

8.5

1.04

1.00 1.02 2.16 3.00 2.03 0.99

8.009 8.005 7.987 7.981 7.844 7.841 7.837 7.821 7.815 7.658 7.653 7.634 7.628 7.611 7.605 7.587 7.582 7.562 7.330 7.325 7.316 7.309 7.298 7.292 7.282 7.278 7.258 7.242 7.235 7.225 7.222 7.209 7.203 7.111 7.104 7.096 4.826 4.817 4.765 4.756 4.293 4.287 4.243 4.232 4.226 4.219 4.196 4.172 1.285 1.261 1.238 0.072 0.000

5a

Current Data Parameters NAME cxy-349-c EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110225 Time 16.50 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 48 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 4096 DW 27.800 usec DE 8.00 usec TE 296.2 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677478 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

160

150

140

130

120

110

100

90

80

70

60

41

50

40

30

20

ppm


O O S N CO2 Et

0.069 -0.000

1.292 1.269 1.245

3.31

2.308

2

1

lrc-5-1 10 1 20110304 16.23 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 16 0 8992.806 0.137219 3.6438515 574.7 55.600 8.00 295.7 1.00000000 1


ppm


14.11

3

82.69 77.48 77.06 76.64

4

21.09

5

3.07

3.27

1.00

4.811 4.803 4.750 4.742 4.284 4.278 4.244 4.220 4.196 4.172

6



52.54

7

61.20

8

140.80 140.26 138.25 137.95 135.98 135.83 133.04 129.87 129.26 127.93 126.67 121.30

9

162.19

10

5.03

0.99 1.02 2.12

8.005 8.000 7.982 7.976 7.837 7.835 7.831 7.814 7.808 7.627 7.622 7.604 7.598 7.580 7.576 7.260 7.098 7.086 7.079

5b

lrc-5-1-c 10 1 20110415 16.46 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 234 4 17985.611 0.274439 1.8219508 2048 27.800 6.50 300.6 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

42

60

50

40

30

20

ppm


O O S N CO2Et

0.072 -0.000

1.296 1.272 1.248

81.77 77.48 77.06 76.64

2

1


0 ppm NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 D11 TD0

14.08

3

lrc-4 21 1 20110302 18.35 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 16 0 8992.806 0.137219 3.6438515 256 55.600 8.00 295.7 1.00000000 1


3.15

4


53.66

5

61.59

6

1.06 2.13

1.00

7

145.95 141.14 139.14 136.11 135.11 133.51 132.35 130.47 127.75 127.47 121.71 118.41 112.34

8 161.96

9

5d

4.841 4.833 4.779 4.772 4.382 4.377 4.321 4.315 4.252 4.228 4.205 4.181

1.02 1.04 4.06 2.04 1.02

8.003 7.999 7.975 7.858 7.852 7.835 7.830 7.705 7.701 7.681 7.676 7.658 7.652 7.633 7.629 7.624 7.609 7.596 7.401 7.372 7.264 7.123 7.117 7.110

NC

lrc-4-c 10 1 20110304 20.50 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 409 4 17985.611 0.274439 1.8219508 11585.2 27.800 8.00 295.3 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

43

70

60

50

40

30

20

ppm


O O S N CO2 Et

Br

6.5

6.0

5.5

5.0

0.000

1.289 1.265 1.241

3.32

1.19 2.10 4.5

3.5

3.0

82.06 77.48 77.06 76.64

4.0

2.5

2.0

1.5

1.0

0.5



ppm 14.07

7.0



53.06

7.5

61.37

8.0

140.94 140.03 139.66 135.98 135.38 133.26 131.62 130.15 128.59 127.63 122.66 121.45

8.5 162.01

9.0

1.00

4.805 4.797 4.744 4.736 4.318 4.312 4.256 4.250 4.244 4.220 4.196 4.173

1.00 0.99 2.03 2.01 2.95

8.000 7.976 7.833 7.810 7.805 7.668 7.663 7.644 7.639 7.619 7.613 7.593 7.589 7.568 7.565 7.436 7.407 7.259 7.129 7.100 7.084

5e

Current Data Parameters NAME cxy-353-3 EXPNO 11 PROCNO 1 F2 - Acquisition Parameters Date_ 20110413 Time 8.14 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 51 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 812.7 DW 27.800 usec DE 6.50 usec TE 298.5 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677507 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

160

150

140

130

120

110

100

90

80

70

60

44

50

40

30

20

ppm


O O S N

CO2 Et

-0.000

1.288 1.264 1.240

3.23

2.289

82.78 77.48 77.06 76.63

3

2

1

0

cxy-lrc-5-2 10 1 20110401 16.19 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 16 0 8992.806 0.137219 3.6438515 228.1 55.600 8.00 296.0 1.00000000 1


ppm 14.09

4

3.01

1.03 2.05

5

21.60

6



52.54

7

61.19

8

140.87 140.71 140.07 138.19 135.89 133.03 129.89 129.27 128.36 127.99 127.37 123.85 121.30

162.15

9

1.00

0.96 0.98 2.01 0.99 1.96 1.95

8.000 7.983 7.977 7.841 7.838 7.834 7.818 7.812 7.656 7.651 7.632 7.627 7.609 7.603 7.585 7.580 7.560 7.556 7.258 7.217 7.191 7.178 7.164 7.108 7.102 7.094 7.087 7.006 7.000 6.992 4.817 4.808 4.756 4.747 4.288 4.282 4.244 4.227 4.220 4.196 4.173

5f


cxy-lrc-5-2-4.20 11 1 20110420 8.20 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 103 4 17985.611 Hz 0.274439 Hz 1.8219508 sec 1290.2 27.800 usec 6.50 usec 299.4 K 2.00000000 sec 0.03000000 sec 1


160

150

140

130

120

110

100

90

80

70

45

60

50

40

30

20

ppm


O O S N CO 2Et CN

5g 8.008 8.005 7.981 7.864 7.863 7.841 7.836 7.693 7.688 7.669 7.663 7.644 7.641 7.605 7.601 7.581 7.576 7.564 7.503 7.481 7.476 7.451 7.426 7.400 7.265 7.130 7.123 7.117 4.838 4.830 4.776 4.769 4.397 4.391 4.335 4.329 4.255 4.231 4.208 4.184 1.301 1.277 1.254 -0.001


4.5

3.11

4.0

3.5

3.0

2.5

2.0

1.5

1.0


14.06

5.0


53.67

5.5

61.59

6.0

81.56 77.48 77.06 76.64

161.89

6.5

1.00 2.08

7.0

7.5

1.00

1.02

8.0

142.60 141.09 139.05 136.19 135.08 133.56 132.00 131.41 130.65 130.50 129.44 127.42 121.74 118.58 112.70

1.01 1.00 4.07 2.09


cxy-370-3.4-c 10 1 20110304 15.55 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 79 4 17985.611 0.274439 1.8219508 9195.2 27.800 8.00 295.9 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

46

60

50

40

30

20

ppm


O O S N CO2 Et F3C

0.081 0.000

1.286 1.262 1.238

3.30 4

3 81.28 77.49 77.06 76.60

2




1

0 ppm NAME EXPNO PROCNO Date_ Time INSTRUM PROBHD PULPROG TD SOLVENT NS DS SWH FIDRES AQ RG DW DE TE D1 D11 TD0

13.97

5


53.98

6

1.01 2.08

4.857 4.850 4.795 4.788 4.464 4.459 4.402 4.397 4.260 4.236 4.212 4.189

1.00

7

CF 3

61.72

8

161.87 143.73 141.27 138.78 136.18 135.04 133.75 132.42 132.09 131.68 131.26 130.76 128.45 127.31 127.16 124.85 122.61 122.49 122.38 121.99 121.37 117.66

9

1.00

1.01 1.98 2.04 2.06

8.040 8.015 7.875 7.851 7.849 7.824 7.765 7.740 7.737 7.716 7.712 7.685 7.659 7.635 7.263 7.140

5h

cxy-371-3.4-c 10 1 20110304 16.07 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 73 4 17985.611 0.274439 1.8219508 11585.2 27.800 8.00 295.9 2.00000000 0.03000000 1



180

170

160

150

140

130

120

110

100

90

80

70

47

60

50

40

30

20

ppm


O O S N

CO 2Et N

8.569 8.555 8.063 8.057 8.034 7.855 7.851 7.832 7.826 7.642 7.636 7.627 7.620 7.611 7.603 7.601 7.580 7.575 7.270 7.222 7.206 7.200 7.197 7.069 7.062 7.055 7.047 7.043 4.874 4.866 4.813 4.806 4.352 4.346 4.292 4.286 4.255 4.232 4.208 4.184 1.297 1.274 1.250 0.079

5i Current Data Parameters NAME cxy-365-3 EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110413 Time 8.20 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zg30 TD 65536 SOLVENT CDCl3 NS 9 DS 0 SWH 8992.806 Hz FIDRES 0.137219 Hz AQ 3.6438515 sec RG 128 DW 55.600 usec DE 8.00 usec TE 298.2 K D1 1.00000000 sec TD0 1

5.5

5.0

4.0

3.16

1.02 2.03

4.5

3.0

83.79 77.48 77.06 76.63

3.5

2.5

2.0

1.5

1.0

0.5

ppm

14.06

6.0


53.53

6.5

61.05

7.0

149.00 139.50 139.44 137.06 135.90 135.73 133.15 130.13 127.96 123.15 121.34 121.23

7.5

1.00

8.0

1.01 1.96

1.00 0.98 3.03

8.5 162.34 159.47

1.01


Current Data Parameters NAME cxy-365-3 EXPNO 11 PROCNO 1 F2 - Acquisition Parameters Date_ 20110413 Time 8.23 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 62 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 574.7 DW 27.800 usec DE 6.50 usec TE 298.5 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677509 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

160

150

140

130

120

110

100

90

80

70

48

60

50

40

30

20

ppm


O O S N Ph

CO2 tBu

7.0

6.5

6.0

5.0

4.5

-0.000

1.419

9.35

1.03

4.763 4.755 4.702 4.695 4.274 4.270 4.214 4.209

5.5

4.0

3.0

2.5

2.0

82.72 82.35 77.59 77.16 76.74

3.5

1.5

1.0

0.5

cxy-653-b-tbu 10 1 20111103 16.22 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 8 0 8992.806 0.137219 3.6438515 71.8 55.600 8.00 298.8 1.00000000 1


ppm


28.07

7.5



52.85

8.0

141.23 140.49 140.01 137.14 136.23 133.08 129.96 128.51 128.34 127.73 126.82 121.41

8.5

161.47

9.0

1.00

1.00 1.03 2.10 3.28 2.07 1.12

7.994 7.969 7.831 7.807 7.624 7.599 7.596 7.595 7.572 7.301 7.294 7.278 7.268 7.250 7.195 7.187 7.179 7.169 6.983

5j

cxy-653-b-tbu 11 1 20111103 16.26 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 46 4 17985.611 0.274439 1.8219508 574.7 27.800 6.50 299.1 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

49

60

50

40

30

ppm


O O S N Ph

CO2 Cy

5

3

6.18

4.15

1.00 4

1

82.79 77.59 77.16 76.74 74.02

2

0

cxy-668-b 10 1 20111117 16.44 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 11 0 8992.806 0.137219 3.6438515 128 55.600 8.00 296.7 1.00000000 1


ppm


31.64 31.47 25.31 23.76 23.69

6



52.83

7

141.05 140.77 140.29 136.27 136.10 133.14 130.01 128.60 128.45 127.94 126.86 121.45

161.71

8

2.06

0.97 1.00 2.07 2.97 2.09 1.02

8.013 8.009 7.991 7.986 7.839 7.832 7.816 7.811 7.628 7.623 7.605 7.599 7.581 7.577 7.308 7.301 7.290 7.284 7.274 7.257 7.224 7.215 7.209 7.198 7.191 7.096 7.089 7.082 4.823 4.808 4.800 4.747 4.739 4.298 4.292 4.237 4.231 1.741 1.724 1.619 1.488 1.478 1.446 1.412 1.376 1.359 1.351 1.343 1.321 1.292 1.287 1.256 -0.000

5k

cxy-668-b 11 1 20111117 16.47 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 63 4 17985.611 0.274439 1.8219508 456.1 27.800 6.50 297.1 2.00000000 0.03000000 1



170

160

150

140

130

120

110

100

90

80

70

50

60

50

40

30

ppm


O O S N Ph

CO2 Bn

6

0.083 0.002

0.98

1.00

5

4

82.78 77.59 77.16 76.74

3

2

1

cxy-653-a-bn 10 1 20111103 16.14 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 10 0 8992.806 0.137219 3.6438515 128 55.600 8.00 298.5 1.00000000 1


0 ppm


52.84

7



67.04

8

141.68 140.84 140.03 136.04 135.55 135.20 133.19 130.06 128.73 128.66 128.59 128.53 128.29 127.91 126.87 121.44

162.02

9

2.14

0.95 1.02 2.08 10.80 1.14

7.933 7.912 7.823 7.804 7.794 7.575 7.564 7.556 7.545 7.337 7.325 7.317 7.302 7.289 7.280 7.266 7.258 7.247 7.235 7.227 7.215 7.203 7.191 7.183 7.134 7.127 7.120 5.174 4.805 4.797 4.744 4.735 4.274 4.268 4.212 4.206

5l

cxy-653-a-bn 11 1 20111103 16.17 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 40 4 17985.611 0.274439 1.8219508 322.5 27.800 6.50 298.9 2.00000000 0.03000000 1



160

150

140

130

120

110

100

90

80

70

51

60

50

40

30

20 ppm


O O S N CO2 tBu

MeO

0.072 0.000

1.438

9.16

3.02 4

2

82.64 82.35 77.58 77.16 76.74

3

1

cxy-663-b 10 1 20111110 16.38 spect 5 mm DUL 13C-1 zg30 65536 CDCl3 13 0 8992.806 0.137219 3.6438515 256 55.600 8.00 298.4 1.00000000 1


ppm


28.17

1.06

5



55.38 52.69

6

113.91

7

140.85 139.85 137.21 136.27 133.48 133.10 129.92 128.19 127.76 121.45

8

161.59 159.55

9

1.00

0.98 1.04 2.15 2.08 1.11 2.08

7.990 7.987 7.964 7.833 7.810 7.805 7.651 7.646 7.626 7.622 7.602 7.596 7.577 7.573 7.552 7.260 7.106 7.083 7.077 6.969 6.962 6.955 6.831 6.824 6.801 4.750 4.742 4.689 4.681 4.269 4.262 4.208 4.202 3.768

5m

cxy-663-b 20 1 20111110 20.58 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 318 4 17985.611 0.274439 1.8219508 322.5 27.800 6.50 298.5 2.00000000 0.03000000 1



160

150

140

130

120

110

100

90

80

70

52

60

50

40

30

ppm


O O S N Ph

CO 2tBu

6.5

6.0

5.0

4.5

4.0

3.0

2.5

0.078 -0.000

1.422

2.0

82.55 82.30 77.58 77.16 76.74

3.5

9.19

2.434

3.05

1.03

4.753 4.745 4.692 4.684 4.258 4.252 4.198 4.192

5.5

1.5

1.0



ppm


22.01

7.0

28.07

7.5



52.89

8.0

144.06 141.35 140.89 139.98 137.20 133.65 130.90 128.47 128.28 127.76 126.87 121.19

8.5

161.55

9.0

1.00

0.99 0.99 1.03 3.28 2.05 1.07

7.757 7.712 7.685 7.392 7.366 7.303 7.279 7.269 7.253 7.195 7.187 7.180 7.169 7.164 6.984 6.978 6.972

5a'

cxy-667 11 1 20111110 16.19 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 31 4 17985.611 0.274439 1.8219508 512 27.800 6.50 298.5 2.00000000 0.03000000 1



160

150

140

130

120

110

100

90

80

70

53

60

50

40

30

ppm


O O S N

CO 2Et

6.5

5.5

5.0

4.5

4.0

3.0

79.08 77.48 77.06 76.64

3.5

3.17

2.16

2.18 6.0

2.5

2.0

1.5




1.0


14.14

7.0


46.04

7.5

61.80

8.0

143.43 142.41 136.14 134.45 134.03 129.85 129.04 128.40 125.46 124.39 124.21 122.46

8.5 160.65

9.0

1.00

1.22 2.09 1.28 2.37 2.24 1.26

7.753 7.726 7.702 7.697 7.691 7.672 7.636 7.632 7.611 7.607 7.585 7.581 7.524 7.521 7.495 7.468 7.441 7.410 7.406 7.383 7.377 7.362 7.357 7.326 7.322 7.318 7.298 7.259 6.346 6.337 6.336 6.327 4.452 4.428 4.416 4.392 4.353 4.330 4.318 4.306 4.294 3.666 3.655 3.605 3.594 3.515 3.507 3.454 3.446 1.410 1.386 1.362 -0.000

4a

cxy-333-4.20 10 1 20110420 8.30 spect 5 mm DUL 13C-1 zgpg30 65536 CDCl3 318 4 17985.611 0.274439 1.8219508 574.7 27.800 6.50 298.8 2.00000000 0.03000000 1



160

150

140

130

120

110

100

90

80

70

54

60

50

40

30

20

ppm


O O S N

CO2 Et

5.0

4.5

4.0

2.5

0.076 -0.000

1.402 1.378 1.355

3.17

2.354

3.18 3.0

79.08 77.48 77.06 76.64

3.5

2.0

1.5

1.0

0.5



ppm 14.12

5.5

2.20

4.447 4.434 4.423 4.411 4.387 4.373 4.363 4.349 4.325 4.313 4.302 4.289 3.670 3.659 3.608 3.597 3.490 3.482 3.429 3.420

2.17 6.0

21.67

6.5



45.97

7.0

61.73

7.5

143.33 142.41 138.78 136.05 134.34 133.99 129.78 129.17 128.84 126.05 124.43 124.38 122.53 122.36

8.0 160.65

8.5

1.00

1.16 1.13 4.22 1.41 1.15

7.740 7.714 7.631 7.606 7.583 7.581 7.514 7.488 7.473 7.466 7.439 7.284 7.261 7.234 7.120 7.095 6.351 6.342 6.332

4f

Current Data Parameters NAME cxy-372-c EXPNO 10 PROCNO 1 F2 - Acquisition Parameters Date_ 20110304 Time 20.42 INSTRUM spect PROBHD 5 mm DUL 13C-1 PULPROG zgpg30 TD 65536 SOLVENT CDCl3 NS 71 DS 4 SWH 17985.611 Hz FIDRES 0.274439 Hz AQ 1.8219508 sec RG 13004 DW 27.800 usec DE 8.00 usec TE 295.3 K D1 2.00000000 sec D11 0.03000000 sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P1 12.50 usec PL1 2.00 dB SFO1 75.4752953 MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD2 100.00 usec PL2 3.00 dB PL12 22.33 dB PL13 23.00 dB SFO2 300.1312005 MHz F2 - Processing parameters SI 32768 SF 75.4677500 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40

160

150

140

130

120

110

100

90

80

70

55

60

50

40

30

20

ppm

Catalytic [2 + 2] and [3 + 2] cycloaddition reactions

Catalytic [2 + 2] and [3 + 2] cycloaddition reactions

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Worksheet #2: Synthesis Reactions