61, No. 4, pp. 661-672, 1989. Printed in Great Britain. 0 1989 IUPAC. Design of low-energy barrier intramolecular ... be met in the case of degenerate rearrangements. Rather .... Stereoprojections of molecular structures of 2-acetoxy-3,5,7-.
Pure & Appl. Chem., Vol. 61, No. 4, pp. 661-672, 1989.
Printed in Great Britain. 0 1989 IUPAC
Design of low-energy barrier intramolecular rearrangements by fitting stereoelectronic requirements of reaction paths Vladimir I. Minkin Institute of Physical and Organic Chemistry, Rostov University, Rostov on Don, SU-344711, USSR
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Abstract A general approach to molecular design of structurally nonrigid compounds capable of fast and reversible intramolecular rearrangements due to migration of the C,N,P,As,S,Se,Te centere? grpups has been developed. High frequencies of migration amounting to 10 s at ambient temperature are achieved by adjusting the initial structure of the rearranged compound to the steric requirements of reaction paths and transition state or intermediate structures for nucleophilic substitution at the central atom of a migratory group through low-energy barrier conformational or polytopal interconversions.
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INTRODUCTION
Intramolecular rearrangements play a remarkable role in organic chemistry, representing key steps of many important reactions. Hence, an understanding of the origin of the factors governing steric courses and heights of the energy barriers of these rearrangements is necessary for a deliberate design of particular reactions. Within the last several years work in our laboratory was directed towards the study of compounds susceptible to fast and reversible rearrangements (1) caused by migration within a molecule of bulky groups formed by nonmetallic elements to the right of carbon in the Periodic Table
(&I
x, Y
0, s, NR Z = CH, CR, N. ( Z ) m = Carbo or heterocycle MRn = C(O)R, Aryl, Hetaryl, NO, NO2, PR2,+PR3, P(0)R2,AsR2, SR, S(O)R, S02R, TeR =
Whereas the rearrangements of this type with hydrogen atom or organometallic fragments have been known for a long time, it was o n l y in the seventies that first examples of the intramolecular displacements of carbon and phosphorus centered groups, occurring on the tautomeric energy scale (2),were documented, for comprehensive reviews see (Refs.l,2). 0 5 kcal mol- 1 A G25
C6H2(N02)3 > SC6H2(N02)3> S(O)R> 3 +SPh2 > PF3Ph > P(-OCH2CH20-) > P(NR)(OR')2 > Pph2 > NO> C(0)CH3> NO2 > S 0 2 k >>Alk Acknowledgements I am grateful to all my colleagues whose names are listed in the corresponding references for their valuable contribution to the investigation presented. REFERENCES
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