Brønsted acid catalyzed asymmetric propargylation of aldehydes.
Brønsted acid catalyzed asymmetric propargylation of aldehydes.
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DOI：
10.1002/anie.201107407
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发表时间：
2012-02-06
影响因子：
16.6
通讯作者：
Antilla, Jon C.
中科院分区：
文献类型：
--
作者：
Jain, Pankaj;Wang, Hao;Houk, Kendall N.;Antilla, Jon C.
对映体纯的高炔丙醇是非常有用的中间体，具有广泛的合成用途。末端炔官能团用作交叉偶联、复分解和杂环合成的合成柄。[1]将联烯或炔丙试剂添加到羰基化合物中在机理上类似于与烯丙试剂的类似反应。虽然存在许多有用的和创新的方法来合成高烯丙醇，[2]高炔丙醇的对映选择性合成仍然困难。两个主要的并发症是1）与烯丙基底物相比，烯丙基和炔丙基底物的反应性较低，和2）与控制反应区域选择性相关的困难。[3]在此，我们描述了一种高对映选择性催化制备高炔丙醇的方法。对该反应的计算研究提供了对该反应的催化和立体化学的深入了解。目前许多对映选择性炔丙基化反应的方法依赖于手性试剂的使用。[4]已经开发了替代的催化方法，但限于使用基于丙二烯或炔丙基金属的试剂或中间体。[2a尽管有显著的工作，但这些方法中的许多方法受到一个或多个限制的限制。其中包括1）使用相对难以制备或对空气不稳定的试剂和/或
Enantiomerically pure homopropargylic alcohols are highly useful intermediates, with broad synthetic utility. The terminal alkyne functionality serves as a synthetic handle for crosscoupling, metathesis, and heterocycle synthesis.[1] The addition of allenic or propargylic reagents to carbonyl compounds is mechanistically similar to the analogous reaction with allylic reagents. Though many useful and innovative methods exist for the synthesis of homoallylic alcohols,[2] the enantio-selective synthesis of homopropargylic alcohols remains arduous. Two main complications are 1) the lower reactivity of the allenylic and propargylic substrates in comparison to allylic substrates, and 2) the difficulties associated with controlling the reaction regioselectivity.[3] Herein, we describe a highly enantioselective catalytic method for the preparation of homopropargylic alcohols. Computational studies of the reaction provide insight into the catalysis and stereochemistry of the reaction.Many current methods for enantioselective propargylation reactions rely upon the use of chiral reagents.[4] Alternative catalytic methods have been developed, but are limited to the use of allenylic or propargylic metal-based reagents or intermediates.[2a, 5] Despite notable work, many of these methods are restricted by one or more limitations. Among them are 1) the use of reagents that are relatively difficult to prepare or are unstable to air and/or
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影响因子：
15
作者：
Chen M;Handa M;Roush WR
通讯作者：
Roush WR
影响因子：
15
作者：
Burgos, CH;Canales, E;Soderquist, JA
通讯作者：
Soderquist, JA
影响因子：
2.1
作者：
Dai, WM;Yeung, KKY;Wang, YQ
通讯作者：
Wang, YQ
影响因子：
5.2
作者：
Francais, Antoine;Leyva, Antonio;Ley, Steven V.
通讯作者：
Ley, Steven V.
影响因子：
5.2
作者：
Chen, Jinshui;Captain, Burjor;Takenaka, Norito
通讯作者：
Takenaka, Norito