Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions.
Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions.
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DOI：
10.1021/acs.accounts.1c00329
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发表时间：
2021-09-07
影响因子：
18.3
通讯作者：
Giri R
中科院分区：
文献类型：
--
作者：
Wickham LM;Giri R
最近，烯烃二碳官能化，即，具有两个碳源的烯烃双官能化的强有力的有机合成方法，作为具有从简单化学品快速合成复杂分子的巨大前景的强大反应而出现。该反应通常用过渡金属（TM）通过烷基金属[β-H-C（sp3）-[M]]物质的碳源拦截来实现，烷基金属[β-H-C（sp3）-[M]]物质是易于经历快速β-H消除的关键中间体。相关的先前报告，因为保罗Chiusoli和Catellani的工作在1982年[四面体快报。1982，23，4517]，已经使用了双环和二取代的末端烯烃，其中通过几何限制或完全缺乏β-H来避免β-H消除。基于β-H-C（sp3）-[M]中间体可以通过第一行晚期TMs和配位辅助的瞬时金属杂环的形成而变得易于拦截的推理，这两种策略被实施以解决烯烃双碳官能化反应中的β-H消除问题.因为第一行后TM催化C（sp3）-C（sp3）偶联，所以预期Cu和Ni赋予在烯烃碳化时催化产生的β-H-C（sp3）-[M]中间体足够的稳定性，用于它们随后在三组分反应中被碳亲电体/亲核体拦截。此外，这种固有性质可以通过熵驱动的环化/偶联反应使烯烃与碳偶联配偶体双官能化。在进行三组分反应时，假设了稳定难处理的β-H-C（sp3）-[M]中间体的环化概念。环化以减少β-H消除的想法基于Whitesides的[J. Am. 1976，98，6521]观察到金属杂环经历β-H消除比无环烷基金属慢得多。在本报告中，烯烃二碳官能化反应的实例表明，Cu和Ni催化剂可以使烯基锌试剂、烷基卤化物和芳基卤化物环化/偶联，得到复杂的碳环和杂环。此外，形成配位辅助的瞬时镍杂环，使区域选择性的性能的三组分的各种烯基化合物的dicarbofunctionalization。[M]-H与β-H消除后生成的烯烃原位反应，引发了前所未有的金属配体收缩过程，其中含金属的六元环收缩为五元环，允许在烯丙基（1，3）位产生新的碳-碳键。讨论了这些区域选择性烯烃双碳官能化反应的应用。
Recently, alkene dicarbofunctionalization, i.e., the powerful organic synthesis method of alkene difunctionalization with two carbon sources, emerged as a formidable reaction with immense promise to synthesize complex molecules expeditiously from simple chemicals. This reaction is generally achieved with transition metals (TMs) through interception by carbon sources of an alkylmetal [β-H–C(sp3)–[M]] species, a key intermediate prone to undergo rapid β-H elimination. Related prior reports, since Paolo Chiusoli and Catellani’s work in 1982 [Tetrahedron Lett. 1982, 23, 4517], have used bicyclic and disubstituted terminal alkenes, wherein β-H elimination is avoided by geometric restriction or complete lack of β-H’s. With reasoning that β-H–C(sp3)–[M] intermediates could be rendered amenable to interception with the use of first row late TMs and formation of coordination-assisted transient metallacycles, these two strategies were implemented to address the β-H elimination problem in alkene dicarbofunctionalization reactions. Because first row late TMs catalyze C(sp3)–C(sp3) coupling, Cu and Ni were anticipated to impart sufficient stability to β-H–C(sp3)–[M] intermediates, generated catalytically upon alkene carbometalation, for their subsequent interception by carbon electrophiles/nucleophiles in three-component reactions. Additionally, such an innate property could enable alkene difunctionalization with carbon coupling partners through entropically driven cyclization/coupling reactions. The cyclometalation concept to stabilize intractable β-H–C(sp3)–[M] intermediates was hypothesized when three-component reactions were performed. The idea of cyclometalation to curtail β-H elimination is founded upon Whitesides’s [J. Am. Chem. Soc. 1976, 98, 6521] observation that metallacycles undergo β-H elimination much slower than acyclic alkylmetals. In this Account, examples of alkene dicarbofunctionalization reactions demonstrate that Cu and Ni catalysts could enable cyclization/coupling of alkenylzinc reagents, alkyl halides, and aryl halides to afford complex carbo- and heterocycles. In addition, forming coordination-assisted transient nickellacycles enabled regioselective performance of three-component dicarbofunctionalization of various alkenyl compounds. In situ reaction of [M]-H with alkenes generated after β-H elimination induced an unprecedented metallacycle contraction process, in which six-membered metal-containing rings shrank to five-membered cycles, allowing creation of new carbon–carbon bonds at allylic (1,3) positions. Applications of these regioselective alkene dicarbofunctionalization reactions are discussed.
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影响因子：
8.4
作者：
Dhungana RK;Sapkota RR;Niroula D;Giri R
通讯作者：
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1.8
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15
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影响因子：
23.5
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通讯作者：
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