Catalyst-Controlled Wacker-Type Oxidation: Facile Access to Functionalized Aldehydes

被引：89

作者：

Wickens, Zachary K. ^{[1
]}

Skakuj, Kacper ^{[1
]}

Morandi, Bill ^{[1
]}

Grubbs, Robert H. ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Arnold & Mabel Beckman Lab Chem Synth, Pasadena, CA 91125 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 03期

基金：

瑞士国家科学基金会;

关键词：

ANTI-MARKOVNIKOV HYDROAMINATION; INTERNAL OLEFINS; SYNTHETIC APPLICATIONS; TERMINAL OLEFINS; MOLECULAR-OXYGEN; ALKENES; EFFICIENT; KETONES; ALCOHOLS; REGIOSELECTIVITY;

D O I：

10.1021/ja411749k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The aldehyde-selective oxidation of alkenes bearing diverse oxygen groups in the allylic and homoallylic position was accomplished with a nitrite-modified Wacker oxidation. Readily available oxygenated alkenes were oxidized in up to 88% aldehyde yield and as high as 97% aldehyde selectivity. The aldehyde-selective oxidation enabled the rapid, enantioselective synthesis of an important pharmaceutical agent, atomoxetine. Finally, the influence of proximal functional groups on this anti-Markovnikov reaction was explored, providing important preliminary mechanistic insight.

引用

页码：890 / 893

页数：4

共 53 条

[1] 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

[2]

Bronner SM, 2014, CHEM SCI, V5, P101, DOI [10.1039/C3SC51897C, 10.1039/c3sc51897c]

[3] Overcoming the "Oxidant Problem": Strategies to Use O2 as the Oxidant in Organometallic C-H Oxidation Reactions Catalyzed by Pd (and Cu) [J].

Campbell, Alison N. ;

Stahl, Shannon S. .

ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (06) :851-863

[4]

Carreira E. M., 2009, Classics in Stereoselective Synthesis

[5] Recent progress in Wacker oxidations: Moving toward molecular oxygen as the sole oxidant [J].

Cornell, Candace N. ;

Sigman, Matthew S. .

INORGANIC CHEMISTRY, 2007, 46 (06) :1903-1909

[6] Wacker-Type Oxidation of Internal Alkenes using Pd(Quinox) and TBHP [J].

DeLuca, Ryan J. ;

Edwards, Jennifer L. ;

Steffens, Laura D. ;

Michel, Brian W. ;

Qiao, Xiaoxiao ;

Zhu, Chunyin ;

Cook, Silas P. ;

Sigman, Matthew S. .

JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (04) :1682-1686

[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] Palladium-Catalyzed Selective Anti-Markovnikov Oxidation of Allylic Esters [J].

Dong, Jia Jia ;

Fananas-Mastral, Martin ;

Alsters, Paul L. ;

Browne, Wesley R. ;

Feringa, Ben L. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (21) :5561-5565

[9] 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

[10]

Feringa B. L., 1986, CHEM COMMUN, P909

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