Catalytic Substrate‐Selective Silylation of Primary Alcohols via Remote Functional‐Group Discrimination
Catalytic Substrate‐Selective Silylation of Primary Alcohols via Remote Functional‐Group Discrimination
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通过远程官能团歧视催化伯醇的底物选择性硅烷化
DOI：
10.1002/anie.202114118
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Kawabata Takeo
中科院分区：
文献类型：
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作者：
Hashimoto Hisashi;Ueda Yoshihiro;Takasu Kiyosei;Kawabata Takeo
通常已知醇的甲硅烷基化发生在空间上最易接近的较少受阻的羟基上。本文报道了伯醇的催化剂控制的底物选择性甲硅烷基化，其中选择性基于空间环境独立于羟基的固有反应性来控制。实现了1，5-氨基醇衍生物的链长选择性甲硅烷基化，并且在催化剂控制条件下，在具有较短或较长链长的类似物存在下，1，5-氨基醇衍生物显示出非常高的反应性。还开发了戊醇类似物的高度底物选择性催化甲硅烷基化，其中在甲硅烷基化时有效地区分来自反应羟基的C（5）处的远程官能度。
Silylation of alcohols has generally been known to take place at the sterically most accessible less‐hindered hydroxy group. Herein, the catalyst‐controlled substrate‐selective silylation of primary alcohols, in which the selectivity was controlled independently of the innate reactivity of the hydroxy group, based on the steric environment, is reported. The chain‐length‐selective silylation of 1,n‐amino alcohol derivatives was achieved and 1,5‐amino alcohol derivatives showed outstandingly high reactivity in the presence of analogues with a shorter or longer chain length under catalyst‐controlled conditions. A highly substrate‐selective catalytic silylation of pentanol analogues was also developed, in which the remote functionality at C(5) from the reacting hydroxy groups was effectively discriminated on silylation.