A cobalt-phosphine complex directed Reformatsky approach to a stereospecific synthesis of the dolastatin 10 unit dolaproine (Dap).
A cobalt-phosphine complex directed Reformatsky approach to a stereospecific synthesis of the dolastatin 10 unit dolaproine (Dap).
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钴-膦复合物引导 Reformatsky 方法立体定向合成多拉司他汀 10 单位多拉脯氨酸 (Dap)。
DOI：
10.1021/jo010530t
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
Grealish,MP
中科院分区：
文献类型：
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作者：
Pettit,GR;Grealish,MP
通过用例如锗3或钐4金属促进的反应代替经典的锌基过程2，用于形成碳-碳键的众所周知的Reformatsky反应已经经历了广泛的改进。对映体纯的恶唑烷酮和醛之间的活化锗3催化的不对称Reformatsky反应已被发现提供了良好的非对映体选择性与（1 S，2 R）-2-氨基-1，2-二苯基乙醇衍生的前体。在锗/手性恶唑烷酮/醛程序可用之前，3我们开始评估与四（三苯基膦）钴（0）5-定向的不对称Reformatsky反应的类似反应，作为目前在II期人类癌症临床试验中的多拉司他汀10（2）6的多拉脯氨酸（1a，Dap）单元的新立体特异性途径。7
The well-known Reformatsky reaction for forming carbon-carbon bonds has been undergoing extensive improvements by replacing the classic zinc-based procedure2 with, eg, germanium3 or samarium4 metalpromoted reactions. The activated germanium3-catalyzed asymmetric Reformatsky reaction between enantiomerically pure oxazolidinones and aldehydes has been found to afford good diastereoselectivity with (1S, 2R)-2-amino-1, 2-diphenylethanol-derived precursors. Prior to availability of the germanium/chiral oxazolidinone/aldehyde procedure, 3 we began to evaluate an analogous reaction with a tetrakis (triphenylphosphine) cobalt (0) 5-directed asymmetric Reformatsky reaction as a new stereospecific route to the dolaproine (1a, Dap) unit of dolastatin 10 (2) 6 now in Phase II human cancer clinical trials. 7