HEXACHLOROACETONE-TRIPHENYLPHOSPHINE - MILD REAGENT FOR THE REGIOSELECTIVE AND STEREOSPECIFIC PRODUCTION OF ALLYLIC CHLORIDES FROM THE ALCOHOLS
HEXACHLOROACETONE-TRIPHENYLPHOSPHINE - MILD REAGENT FOR THE REGIOSELECTIVE AND STEREOSPECIFIC PRODUCTION OF ALLYLIC CHLORIDES FROM THE ALCOHOLS
复制标题
DOI：
10.1021/jo01317a011
复制
发表时间：
1979-01-01
影响因子：
3.6
通讯作者：
ALLEN, TG
中科院分区：
文献类型：
--
作者：
MAGID, RM;FRUCHEY, OS;ALLEN, TG
烯丙醇1-16与六氯丙酮/三苯基膦在10-15℃下反应不到20分钟，生成相应的氯化物。分离只需通过闪蒸即可完成。这种转换发生时，双键的几何形状完全保留，而旋光性醇的构型反转率为bbbb99 % 8。所有的伯醇和仲醇主要生成未重排的氯化物，a/y攻击比为bbb90：除9、12、13和14外，其余的都< 10；只有叔醇的产物大多是重排的。对于高取代体系，二烯的消除成为一个重要的副反应。
Allylic alcohols 1-16 react with hexachloroacetone/triphenylphosphine in less than 20 min at 10-15 C to produce excellent yields of the corresponding chlorides. Isolation is accomplished simply by flash distillation. The con-version occurs with total preservation of double bond geometry and with> 99% inversion of configuration for optically active alcohol 8. All of the primary and secondary alcohols give predominantly the unrearranged chloride, the a/y attack ratio being> 90:< 10 for all but 9, 12, 13, and 14; only the tertiary alcohols give mostly rearranged prod-uct. With more highly substituted systems, elimination to diene becomes an important side reaction.