使用阿赫马托维茨反应制备η³-吡喃基和η³-吡啶基有机金属对映体支架的实用、可扩展、高通量方法。
Practical, scalable, high-throughput approaches to eta3-pyranyl and eta3-pyridinyl organometallic enantiomeric scaffolds using the Achmatowicz reaction.
作者信息
Coombs Thomas C, Lee Maurice D, Wong Heilam, Armstrong Matthew, Cheng Bo, Chen Wenyong, Moretto Alessandro F, Liebeskind Lanny S
机构信息
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
出版信息
J Org Chem. 2008 Feb 1;73(3):882-8. doi: 10.1021/jo702006z. Epub 2008 Jan 3.
Abstract
A unified strategy for the high-throughput synthesis of multigram quantities of the eta(3)-oxopyranyl- and eta(3)-oxopyridinylmolybdenum complexes TpMo(CO)(2)(eta(3)-oxopyranyl) and TpMo(CO)(2)(eta(3)-oxopyridinyl) is described (Tp = hydridotrispyrazolylborato). The strategy uses the oxa- and aza-Achmatowicz reaction for the preparation of these organometallic enantiomeric scaffolds, in both racemic and high enantiopurity versions.
摘要
描述了一种用于高通量合成多克量的η(3)-氧代吡喃基和η(3)-氧代吡啶基钼配合物TpMo(CO)₂(η(3)-氧代吡喃基)和TpMo(CO)₂(η(3)-氧代吡啶基)的统一策略（Tp = 氢化三吡唑基硼酸盐）。该策略使用氧杂和氮杂阿赫马托维奇反应来制备这些有机金属对映体支架，包括外消旋体和高对映体纯度的形式。
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Practical, scalable, high-throughput approaches to eta3-pyranyl and eta3-pyridinyl organometallic enantiomeric scaffolds using the Achmatowicz reaction.使用阿赫马托维茨反应制备η³-吡喃基和η³-吡啶基有机金属对映体支架的实用、可扩展、高通量方法。
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5
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6
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7
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