Visible-Light-Mediated Anti-Markovnikov Hydration of Olefins

被引：96

作者：

Hu, Xia ^{[1
]}

Zhang, Guoting ^{[1
]}

Bu, Faxiang ^{[1
]}

Lei, Aiwen ^{[1
,2
]}

机构：

[1] Wuhan Univ, Inst Adv Studies, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China

[2] Chinese Acad Sci, Lanzhou Inst Chem Phys, Lanzhou 730000, Peoples R China

来源：

ACS CATALYSIS | 2017年 / 7卷 / 02期

基金：

高等学校博士学科点专项科研基金; 中国国家自然科学基金;

关键词：

photochemistry; hydration; anti-Markovnikov; alkene; alcohol; radical; RH/RU DUAL CATALYST; PHOTOREDOX CATALYSIS; ORGANIC-SYNTHESIS; TANDEM HYDROFORMYLATION/HYDROGENATION; HYDROFUNCTIONALIZATION REACTIONS; SYNTHETIC APPLICATIONS; TERMINAL OLEFINS; PRIMARY ALCOHOLS; ALKENES; NUCLEOPHILE;

D O I：

10.1021/acscatal.6b03388

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Considering that stoichiometric borane and oxidant are required in the classical alkene anti-Markovnikov hydration process, it remains appealing to achieve the transformation in a catalytic protocol. Herein, a visible-light mediated anti-Markovnikov addition of water to alkenes by using an organic photoredox catalyst in conjunction with a redox-active hydrogen atom donor was developed, which avoided the need for a transition-metal catalyst, stoichiometric borane, as well as oxidant. Both terminal and internal olefins are readily accommodated in this transformation to obtain corresponding primary and secondary alcohols in good yields with single regioselectivity. This procedure can be scaled up to gram scale with a 230 turnover number based on photocatalyst.

引用

页码：1432 / 1437

页数：6

共 37 条

[1]

[Anonymous], 2013, MARCHS ADV ORGANIC C

[2] Photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction .12. Factors controlling the regiochemistry of the reaction with alcohol as the nucleophile [J].

Arnold, DR ;

Chan, MSW ;

McManus, KA .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1996, 74 (11) :2143-2166

[3] Catalytic Markovnikov and anti-Markovnikov functionalization of alkenes and alkynes: Recent developments and trends [J].

Beller, M ;

Seayad, J ;

Tillack, A ;

Jiao, H .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (26) :3368-3398

[4] Redox Economy in Organic Synthesis [J].

Burns, Noah Z. ;

Baran, Phil S. ;

Hoffmann, Reinhard W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (16) :2854-2867

[5] Allylic C-H Acetoxylation with a 4,5-Diazafluorenone-Ligated Palladium Catalyst: A Ligand-Based Strategy To Achieve Aerobic Catalytic Turnover [J].

Campbell, Alison N. ;

White, Paul B. ;

Guzei, Ilia A. ;

Stahl, Shannon S. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (43) :15116-15119

[6] Supramolecular Catalyst for Aldehyde Hydrogenation and Tandem Hydroformylation-Hydrogenation [J].

Diab, Lisa ;

Smejkal, Tomas ;

Geier, Jens ;

Breit, Bernhard .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (43) :8022-8026

[7] Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis [J].

Dong, Guangbin ;

Teo, Peili ;

Wickens, Zachary K. ;

Grubbs, Robert H. .

SCIENCE, 2011, 333 (6049) :1609-1612

[8] Tandem reaction sequences under hydroformylation conditions:: New synthetic applications of transition metal catalysis [J].

Eilbracht, P ;

Bärfacker, L ;

Buss, C ;

Hollmann, C ;

Kitsos-Rzychon, BE ;

Kranemann, CL ;

Rische, T ;

Roggenbuck, R ;

Schmidt, A .

CHEMICAL REVIEWS, 1999, 99 (11) :3329-3365

[9] ABSOLUTE RATE EXPRESSIONS FOR THE ABSTRACTION OF HYDROGEN BY PRIMARY, SECONDARY, AND TERTIARY ALKYL RADICALS FROM THIOPHENOL [J].

FRANZ, JA ;

BUSHAW, BA ;

ALNAJJAR, MS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (01) :268-275

[10] Electron-transfer state of 9-mesityl-10-methylacridinium ion with a much longer lifetime and higher energy than that of the natural photosynthetic reaction center [J].

Fukuzumi, S ;

Kotani, H ;

Ohkubo, K ;

Ogo, S ;

Tkachenko, NV ;

Lemmetyinen, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (06) :1600-1601

← 1 2 3 4 →