P(MeNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N: An Efficient Catalyst for the Desilylation of <i>tert</i>-Butyldimethylsilyl Ethers
作者:Zhengkun Yu、John G. Verkade
DOI:10.1021/jo991591i
日期:2000.4.1
in 68-94% yield in the presence of 0.2-0.4 equiv of P(MeNCH2CH2)3N. Using P(i-PrNCH2-CH2)3N as the catalyst, 85-97% yields of desilylated alcohols were obtained from TBDMS ethers of 1-octanol, 2-phenoxyethanol, and racemic alpha-phenyl ethanol. These are the first examples of desilylations of silyl ethers catalyzed by nonionic bases. Both catalysts were much less effective for the desilylation of t
伯醇,仲醇和叔醇的叔丁基二甲基甲硅烷基(TBDMS)醚和酚类TBDMS醚分别在DMSO中,80摄氏度,0.2-0.2%的存在下被甲硅烷基化为相应的醇和酚。 0.4当量的P(MeNCH2CH2)3N。使用P(i-PrNCH2-CH2)3N作为催化剂,从1-辛醇,2-苯氧基乙醇和外消旋α-苯基乙醇的TBDMS醚中获得85-97%的去甲硅烷基化醇产率。这些是非离子碱催化的甲硅烷基醚的脱甲硅烷基化的第一个例子。在与用于TBDMS醚相同的条件下,两种催化剂对叔丁基二苯基甲硅烷基(TBDPS)醚的甲硅烷基化的效率都低得多(产率22-45%)。