Modular Construction of Protected 1,2/1,3-Diols, -Amino Alcohols, and -Diamines via Catalytic Asymmetric Dehydrative Allylation: An Application to Synthesis of Sphingosine
Modular Construction of Protected 1,2/1,3-Diols, -Amino Alcohols, and -Diamines via Catalytic Asymmetric Dehydrative Allylation: An Application to Synthesis of Sphingosine
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DOI：
10.1021/acs.joc.7b01181
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发表时间：
2017-09-01
影响因子：
3.6
通讯作者：
Kitamura, Masato
中科院分区：
文献类型：
--
作者：
Tanaka, Shinji;Gunasekar, Ramachandran;Kitamura, Masato
开发了一种新的对映选择性催化方法，用于从δ-或λ-OH/NHBoc-取代的烯丙醇和“H2C=O”/“H2C=NBoc”一步构建1,2-和1,3-OH和/或NH官能团的亚甲基桥手性模块。原位生成的 CH2OH 或 CH(2)NHBoc 质子亲核试剂可在分子内进行烯丙基化，以高产率和对映选择性提供八种可能的配备有乙烯基的 1,2- 或 1,3-O,O、-O,N、-N,O 和 -N,N 手性模块。该方法的实用性已在鞘氨醇的五步合成中得到证明。
A new enantioselective catalysis has been developed for the one-step construction of methylene-bridged chiral modules of 1,2- and 1,3-OH and/or NH function(s) from delta- or lambda-OH/NHBoc-substituted allylic alcohols and "H2C=O"/"H2C=NBoc". A protonic nucleophile, either in situ-generated CH2OH or CH(2)NHBoc, is intramolecularly allylated to furnish eight possible 1,2- or 1,3-O,O, -O,N,-N,O, and -N,N chiral modules equipped with an ethenyl group in high yields and enantioselectivities. The utility of this method has been demonstrated in the five-step synthesis of sphingosine.