The Mechanism of Copper‐Catalyzed Trifunctionalization of Terminal Allenes
The Mechanism of Copper‐Catalyzed Trifunctionalization of Terminal Allenes
复制标题
铜催化末端八烯三官能化的机理
DOI：
10.1002/chem.201900673
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Baik, Mu‐Hyun
中科院分区：
文献类型：
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作者：
Kim, Hong Ki;Mane, Manoj V.;Montgomery, John;Baik, Mu‐Hyun
基于与双（频哪醇）二硼（B2 pin 2）和N-氰基-N-苯基-对甲苯磺酰胺（NCTS）的二硼化/氰化反应，建立了高选择性的铜催化联烯三官能化反应。Cu催化的末端联烯的三官能化由三个催化反应（第一次硼铜化、亲电氰化和第二次硼铜化）组成，其提供具有区域选择性、化学选择性和非对映选择性的密集官能化产物。丙二烯底物具有多个反应位点，并且选择性由合适的相互作用（例如，电子和空间需求）。我们采用DFT计算来理解级联铜催化的末端联烯的三官能化，以高产率提供具有出色的区域选择性、化学选择性和非对映选择性的密集官能化有机分子。通过系统的计算研究解决了累积π系统所带来的选择性挑战;这些研究深入了解了催化多官能化策略，并解释了我们在这些反应中看到的高选择性。
A highly selective copper‐catalyzed trifunctionalization of allenes has been established based on diborylation/cyanation with bis(pinacolato)diboron (B2pin2) andN‐cyano‐N‐phenyl‐p‐toluenesulfonamide (NCTS). The Cu‐catalyzed trifunctionalization of terminal allenes is composed of three catalytic reactions (first borocupration, electrophilic cyanation, and second borocupration) that provide a densely functionalized product with regio‐, chemo‐ and diastereoselectivity. Allene substrates have multiple reaction‐sites, and the selectivities are determined by the suitable interactions (e.g., electronic and steric demands) between the catalyst and substrates. We employed DFT calculations to understand the cascade copper‐catalyzed trifunctionalization of terminal allenes, providing densely‐functionalized organic molecules with outstanding regio‐, chemo‐ and diastereoselectivity in high yields. The selectivity challenges presented by cumulated π‐systems are addressed by systematic computational studies; these give insight to the catalytic multiple‐functionalization strategies and explain the high selectivities that we see for these reactions.