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

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概要

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• 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.

• 社団法人日本薬学会の論文
• 1973-09-25

著者

• 柴崎 正勝

  東大院薬

• 柴崎 正勝

  Faculty Of Pharmaceutical Sciences Teikyo University:(present Address)faculty Of Pharmacertical Scie

• 山田 俊一

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 佐藤 忠夫

  Faculty Of Pharmaceutical Sciences Chiba University

• 山田 俊一

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 寺島 孜郎

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 柴崎 正勝

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 大橋 尚仁

  東大薬

• 寺島 孜郎

  (財)相模中央化学研究所

• 大橋 尚仁

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 寺島 孜郎

  Faculty Of Pharmaceutical Sciences University Of Tokyo:(present Address)sagami Chemical Research Cen

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