Umpolung of .pi.-allylpalladium intermediates. A chemoselective reductive elimination of diols
Umpolung of .pi.-allylpalladium intermediates. A chemoselective reductive elimination of diols
复制标题
π-烯丙基钯中间体的分解。
DOI：
10.1021/jo00239a055
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发表时间：
1988
影响因子：
3.6
通讯作者：
G. Tometzki
中科院分区：
文献类型：
--
作者：
B. Trost;G. Tometzki
通过使用催化量的Pd（0）络合物，烯二醇的二碳酸酯经历还原消除以形成共轭二烯，其中从碳酸酯或亚磷酸三异丙酯释放的醇盐用作化学计量的还原剂。先生：由于羰基加成对于CC键形成反应的重要性和作为起始材料的碳水化合物的丰富性，脱氧方法已成为合成的有力工具。1，2基于钯的简单脱氧方法通常需要氢化物源、电解或低价金属还原剂。[4]我们希望报道Pd（0）配合物能在非常温和的条件下催化烯二碳酸酯的还原裂解，无论是在没有任何外源还原剂的情况下，还是在有亚磷酸酯存在的情况下。5反应似乎涉及-ally 1-
The dicarbonates of enediols undergoreductive elimination to form conjugated dienes by using a catalytic amount of a Pd (0) complex wherein either the alkoxide liberated from the carbonate or triisopropyl phosphite serves as a stoichiometric reducing agent.Sir: Due to the importanceof carbonyl additions for CC bond-forming reactions and the abundance of carbohydrates as starting materials, methods for deoxygenation have become powerful tools for synthesis. 1, 2 Palladium-based methods for simpledeoxygenation have normally required a hydride source, 3 electrolysis, or a low-valent metal reductant. 4 We wish to report that Pd (0) complexes can catalyze the reductive cleavage of enedicarbonates under very mild conditions either inthe absence of any exogenous reducing agent or in the presence of a phosphite. 5 The reactions appear to involve the-ally 1-