Enantioselective Heck–Matsuda Arylations through Chiral Anion Phase‐Transfer of Aryl Diazonium Salts,Angewandte Chemie International Edition

当前位置： X-MOL 学术 › Angew. Chem. Int. Ed. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Enantioselective Heck–Matsuda Arylations through Chiral Anion Phase‐Transfer of Aryl Diazonium Salts
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2017-04-18 , DOI: 10.1002/anie.201702107
Carolina M Avila ₁ , Jigar S Patel ₁ , Yernaidu Reddi ₂ , Masato Saito ₁ , Hosea M Nelson _{1,

3} , Hunter P Shunatona ₁ , Matthew S Sigman ₄ , Raghavan B Sunoj ₂ , F Dean Toste ₁

Affiliation

A mild, asymmetric Heck–Matsuda reaction of five‐, six‐ and seven‐membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd⁰ 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.

中文翻译：

通过芳基重氮盐的手性阴离子相转移进行对映选择性 Heck-Matsuda 芳基化

提出了五元、六元和七元环烯烃与芳基重氮盐的温和、不对称 Heck-Matsuda 反应。^{使用 Pd 0}和手性阴离子助催化剂实现了高产率和对映选择性，后者充当手性阴离子相转移（CAPT）试剂。对于某些底物类别，对手性阴离子催化剂进行调节以最大程度地减少不需要的副产物的形成。更具体地说，BINAM 衍生的磷酸催化剂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，产物选择性的增加是由于所需途径的激活势垒的手性阴离子依赖性降低所致。

更新日期：2017-04-18

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南