Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide

被引：634

作者：

Fu, Ming-Chen ^{[1
]}

Shang, Rui ^{[1
,2
]}

Zhao, Bin ^{[1
]}

Wang, Bing ^{[1
]}

Fu, Yao ^{[1
]}

机构：

[1] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Anhui Prov Key Lab Biomass Clean Energy, CAS Key Lab Urban Pollutant Convers,iChEM, Hefei 230026, Anhui, Peoples R China

[2] Univ Tokyo, Dept Chem, Sch Sci, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1130033, Japan

来源：

SCIENCE | 2019年 / 363卷 / 6434期

基金：

中国国家自然科学基金; 国家重点研发计划;

关键词：

OXIDATION-REDUCTION REACTIONS; CHARGE-TRANSFER STATES; ELECTRON-TRANSFER; PHOTOREDOX CATALYSIS; ARYL IODIDES; ENERGY; PHOTOCHEMISTRY; RADICALS; HALIDES; RATES;

D O I：

10.1126/science.aav3200

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light-emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky's N-alkylpyridinium salts and trifluoromethylation using Togni's reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.

引用

页码：1429 / +

页数：185

共 65 条

[31] Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature [J].