Stereochemical Studies. XXIII. Stereochemistry of the Thermal Isocyanide-Cyanide Rearrangement

DOI Web Site

この論文をさがす

抄録

Thermal rearrangements of R(+)-2-(2-carboethoxy-1-phenyl) propyl isocyanide (R(+)-VIII), S(+)-2-(2-methyl-1-phenyl) butyl isocyanide (S(+)-XVI) and R(+)-2-(2-phenyl) butyl isocyanide (R(+)-XXVIII), were carried out under several reaction conditions. Although the reflux of a diphenyl ether solution of R (+)-VIII or heating R(+)-VIII without solvent afforded almost completely racemized cyanide (S (+)-X) (at most 9% retention of configuration) as the sole reaction product in excellent yields, treatment of S (+)-XVI with a procedure similar to that used with R (+)-VIII gave S (+)-cyanide (S (+)-XXIII) with 90% (reflux of a diphenyl ether solution) and 47% (heating without solvent) retention of configuration. The thermal reaction of R(+)-XXVIII gave three different olefins (XXXIV, XXXV, and XXXVI), in addition to the normal reaction product (R(+)-XXIX) with a low retention of configuration (at most 19%). These observations were discussed from various aspects including the effect of asymmetric solvation due to diphenyl ether and the relative stability of the radical intermediates formed.

収録刊行物

キーワード

詳細情報 詳細情報について

問題の指摘

ページトップへ