New preparative methods for allylic boronates and their application in stereoselective catalytic allylborations
New preparative methods for allylic boronates and their application in stereoselective catalytic allylborations
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DOI：
10.1351/pac200880050913
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发表时间：
2008-05-01
影响因子：
1.8
通讯作者：
Hall, Dennis G.
中科院分区：
文献类型：
--
作者：
Hall, Dennis G.
烯丙型金属试剂向羰基化合物的立体控制加成构成了有机合成中最有用的一类转化。最近发展的刘易斯和布朗斯台德酸催化歧管的烯丙基硼化羰基化合物打开了大门，一个理想的羰基烯丙基化方法，使用稳定和无毒的烯丙基硼酸酯作为试剂。本文介绍了酸催化烯丙基硼化反应的发展，这些新工艺的机理研究，以及正在进行的努力一般催化不对称烯丙基硼化方法。讨论了光学富集的α-取代烯丙基硼酸酯试剂的制备及其在刘易斯酸催化加成反应中的应用，以提供不同的产物，如丙酸酯单元，多取代呋喃，乙烯基环丙烷和较大的环系统。
Stereocontrolled additions of allylic metal reagents to carbonyl compounds constitute one of the most useful classes of transformations in organic synthesis. The recent development of Lewis and Bronsted acid-catalyzed manifolds for the allylboration of carbonyl compounds has opened doors toward an ideal carbonyl allylation methodology using stable and nontoxic allylic boronates as reagents. This paper describes the development of acid-catalyzed allylborations, mechanistic investigations of these new processes, and ongoing efforts toward general catalytic enantioselective allylboration methodologies. The preparation of optically enriched a-substituted allylic boronate reagents is discussed, as well as their applications in Lewis acid-catalyzed additions to afford skeletally diverse products like propionate units, polysubstituted furans, vinylcyclopropanes, and larger ring systems.