Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts.
Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts.
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DOI：
10.1002/anie.201702107
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发表时间：
2017-05-15
期刊：
影响因子：
--
通讯作者：
Toste FD
中科院分区：
文献类型：
--
作者：
Avila CM;Patel JS;Reddi Y;Saito M;Nelson HM;Shunatona HP;Sigman MS;Sunoj RB;Toste FD
提出了五元、六元和七元环烯烃与芳基重氮盐的不对称Heck-Matsuda反应。使用Pd(0)和手性阴离子共催化剂（后者作为手性阴离子相转移（CAPT）试剂）获得了高收率和对映选择性。对于某些底物类别，手性阴离子催化剂被调节，以尽量减少不希望的副产物的形成。更具体地说，binam衍生的磷酸催化剂被证明可以防止环戊烯和环庚烯原料中的烯烃异构化。DFT（B3LYP-D3）计算表明，由于手性阴离子依赖性降低了所需途径的激活势垒，产物选择性增加。利用手性阴离子相转移（CAPT）催化，建立了环戊烯、环己烯和环庚烯衍生物的不对称Heck-Matsuda反应。这些研究表明，CAPT催化可以用来控制Heck-Matsuda的对映选择性和化学选择性
A mild, asymmetric Heck–Matsuda reaction of five-, six- and seven-membered ring alkenes and aryldiazonium salts is presented. High yields and enantioselectivities were achieved using Pd(0) and chiral anion co-catalysts, the latter functioning as a chiral anion phase-transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by-products. More specifically, BINAM-derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP-D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway. An asymmetric Heck-Matsuda reaction of cyclopentene, cyclohexene, and cycloheptene derivatives has been developed using a Chiral Anion Phase Transfer (CAPT) Catalysis. These studies demonstrate that CAPT catalysis can be employed to control the enantio- and chemoselectivity of the Heck-Matsuda
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