Cyclization/Oxygenation Scheme for the Conversion of Polyenes into C3-Oxygenated Polycycles

被引：7

作者：

Geier, Michael J. ^{[1
]}

Gagne, Michel R. ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Caudill Labs, Chapel Hill, NC 27599 USA

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 02期

基金：

加拿大自然科学与工程研究理事会;

关键词：

METAL-MEDIATED FORMATION; REDUCTIVE ELIMINATION; ELECTRON-TRANSFER; OXIDATIVE CLEAVAGE; CYCLIZATION; COMPLEXES; MECHANISMS; CARBON; ALKYL; RADICALS;

D O I：

10.1021/om400003c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Oxidatively induced halogenation and oxygenation reactions of complex Pt(II) organometallic complexes provide a route to a catalytic cation-olefin cyclization/oxygenation sequence. The evidence suggests the involvement of a Pt(III) intermediate, which reacts homolytically to generate an organic free radical that can be intercepted by O-2 followed by the Russell breakdown of the resulting alkyl peroxy radicals or by CuX2 (X = Br, Cl) to yield the X-R product.

引用

页码：380 / 383

页数：4

共 58 条

[1] Electron-poor benzonitriles as labile, stabilizing ligands in asymmetric catalysis [J].

Becker, JJ ;

Van Orden, LJ ;

White, PS ;

Gagné, MR .

ORGANIC LETTERS, 2002, 4 (05) :727-730

[2] Reactions of Late Transition Metal Complexes with Molecular Oxygen [J].

Boisvert, Luc ;

Goldberg, Karen I. .

ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (06) :899-910

[3] Insertion of Molecular Oxygen into a Palladium(II) Methyl Bond: A Radical Chain Mechanism Involving Palladium(III) Intermediates [J].

Boisvert, Luc ;

Denney, Melanie C. ;

Hanson, Susan Kloek ;

Goldberg, Karen I. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (43) :15802-15814

[4] ELECTRON-TRANSFER PROCESSES IN ORGANOPLATINUM COMPLEXES - OXIDATION AND CLEAVAGE OF DIALKYLPLATINUM(II) WITH HEXACHLOROIRIDATE(IV) [J].

CHEN, JY ;

KOCHI, JK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (05) :1450-1457

[5] Driving Catalyst Reoxidation in Wacker Cyclizations with Acetal-Based Metal-Hydride Abstractors [J].

Cochrane, Nikki A. ;

Brookhart, Maurice S. ;

Gagne, Michel R. .

ORGANOMETALLICS, 2011, 30 (09) :2457-2460

[6] Chemical redox agents for organometallic chemistry [J].

Connelly, NG ;

Geiger, WE .

CHEMICAL REVIEWS, 1996, 96 (02) :877-910

[7] Concerted reductive coupling of an alkyl chloride at Pt(IV) [J].

Crosby, Sarah H. ;

Thomas, Helen R. ;

Clarkson, Guy J. ;

Rourke, Jonathan P. .

CHEMICAL COMMUNICATIONS, 2012, 48 (46) :5775-5777

[8] Reversibility effects on the stereoselectivity of Pt(II)-Mediated cascade poly-ene cyclizations [J].

Feducia, Jeremiah A. ;

Gagne, Michel R. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (02) :592-599

[9] ENERGETICS AND MECHANISMS OF CARBON-CARBON AND CARBON-IODIDE REDUCTIVE ELIMINATION FROM A PT(IV) CENTER [J].

GOLDBERG, KI ;

YAN, JY ;

BREITUNG, EM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (26) :6889-6896

[10] Insertion of Dioxygen into a Platinum(II)-Methyl Bond To Form a Platinum(II) Methylperoxo Complex [J].

Grice, Kyle A. ;

Goldberg, Karen I. .

ORGANOMETALLICS, 2009, 28 (04) :953-955

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