A convenient method for the preparation of (Z)-alpha,beta-unsaturated carbonyl compounds
A convenient method for the preparation of (Z)-alpha,beta-unsaturated carbonyl compounds
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DOI：
10.1021/jo952098j
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发表时间：
1996-04-19
影响因子：
3.6
通讯作者：
Geremia, JM
中科院分区：
文献类型：
--
作者：
Taber, DF;Herr, RJ;Geremia, JM
(Z)-R不饱和羰基化合物2是有机合成中重要的结构单元。2已经开发了几种方法用于这些化合物的一般合成，3其中一些已知表现出显著的（Z）-选择性（> 90%）。4 Ganem已经表明，R-重氮酯1用乙酸铑（II）进行氢化物消除以产生（Z）-烯酸酯2，5，但仅在不可能竞争1，5-插入的情况下（等式1）。6，7我们已经发现，反应性更强的三氟乙酸铑（II）络合物在低温下有效地催化氢化物消除过程，而不形成碳环（3）。
(Z)-R,-Unsaturated carbonyl compounds 2 are important building blocks in organic synthesis. 2 Several procedures have been developed for the general synthesis of these compounds, 3 a few of which are known to exhibit substantial (Z)-selectivity (> 90%). 4 Ganem has shown that R-diazo esters 1 undergo-hydride elimination with rhodium (II) acetate to produce (Z)-enoates 2, 5 but only in cases where no competing 1, 5-insertion was possible (eq 1). 6, 7 We have found that the more reactive rhodium (II) trifluoroacetate complex efficiently catalyzes the-hydride elimination process, at low temperatures, without carbocycle (3) formation.