Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities.
Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities.
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DOI：
10.1002/anie.201507152
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发表时间：
2015-12-21
影响因子：
16.6
通讯作者：
Denmark, Scott E.
中科院分区：
文献类型：
--
作者：
Cresswell, Alexander J.;Eey, Stanley T. -C.;Denmark, Scott E.
尽管近年来在烯烃的催化、对映选择性卤代官能化的发展方面取得了重大进展，但用于提供对映体富集的邻二卤化物产物的相关烯烃二卤化仍然相对不发达。然而，越来越多的复杂天然产物在立体中心带有卤素原子，凸显了合成化学家的武器库中的这一关键差距。本综述强调了对映选择性二卤化过程设计中固有的选择性挑战，并制定了基于机制的烯烃二卤化分类，包括那些可能规避“经典”haliranium（或烯烃二卤π络合物）中间体的分类。讨论了用于烯烃二氯化或二溴化的各种金属和主族卤化物试剂，并对这些转化的拟议机制进行了严格评估。在不同活化模式下控制二卤素加成的绝对和相对立体化学过程的烯烃二卤化催化是立体选择性合成中最棘手的问题之一。绕过“经典”haliranium（或烯烃-二卤π配合物）中间体的二卤化反应为催化提供了新的、令人兴奋的机会，可能对立体选择性烯烃双官能化的设计产生更广泛的影响。
Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations of alkenes, the related dihalogenation of olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, the growing number of complex natural products bearing halogen atoms at stereogenic centers has underscored this critical gap in the synthetic chemist’s arsenal. This Review highlights the selectivity challenges inherent in the design of enantioselective dihalogenation processes, and formulates a mechanism-based classification of alkene dihalogenations, including those that may circumvent the “classical” haliranium (or alkene-dihalogen π-complex) intermediates. A variety of metal and main group halide reagents that have been used for the dichlorination or dibromination of alkenes are discussed, and the proposed mechanisms of these transformations are critically evaluated. Catalysis of alkene dihalogenation , under different activation modes, with control over both the absolute and relative stereochemical course of dihalogen addition, is one of the most vexing problems in stereoselective synthesis. Dihalogenations that circumvent the “classical” haliranium (or alkene-dihalogen π complex) intermediates provide new and exciting opportunities for catalysis, potentially having broader implications for the design of stereoselective alkene difunctionalizations.
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影响因子：
3.6
作者：
ARGANBRIGHT, RP;YATES, WF
通讯作者：
YATES, WF
DOI：
10.1039/j19680001417
发表时间：
1968-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL
影响因子：
--
作者：
BALL, MC;COULTARD, RF
通讯作者：
COULTARD, RF
影响因子：
2.1
作者：
BELLESIA, F;GHELFI, F;PINETTI, A
通讯作者：
PINETTI, A
影响因子：
2.1
作者：
BELLUCCI, G;BERTI, G;MARSILI, A
通讯作者：
MARSILI, A
影响因子：
15
作者：
ANDREWS, LJ;KEEFER, RM
通讯作者：
KEEFER, RM