LITHIUM ALKOXIDES OF CINCHONA ALKALOIDS AS CHIRAL CONTROLLERS FOR ENANTIOSELECTIVE ACETYLIDE ADDITION TO CYCLIC N-ACYL KETIMINES
LITHIUM ALKOXIDES OF CINCHONA ALKALOIDS AS CHIRAL CONTROLLERS FOR ENANTIOSELECTIVE ACETYLIDE ADDITION TO CYCLIC N-ACYL KETIMINES
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DOI：
10.1021/jo00111a016
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发表时间：
1995-03-24
影响因子：
3.6
通讯作者：
GRABOWSKI, EJJ
中科院分区：
文献类型：
--
作者：
HUFFMAN, MA;YASUDA, N;GRABOWSKI, EJJ
以奎宁的锂醇盐作为化学计量比的手性添加剂，可以实现对环N-酰基酮亚胺1的高对映选择性的乙酰基加成反应。奎尼丁可以用来生成相反的对映体。温度的优化至关重要，温度过低或过高都会降低选择性。使用亚胺末端的大体积9-苯甲基保护基团，获得了97%的ee，并将其应用于HIV逆转录酶抑制剂3的不对称合成。
Highly enantioselective acetylide addition to cyclic N-acyl ketimines 1 can be carried out using the lithium alkoxide of quinine as a stoichiometric chiral additive. Quinidine can be used to give the opposite enantiomer. Optimization of temperature is critical, with low or high temperatures reducing selectivity. Using the bulky 9-anthrylmethyl protecting group at a distal position on the imine, a 97% ee was achieved and applied to the asymmetric synthesis of HIV reverse transcriptase inhibitor 3.