Rollover-Assisted C( sp2) -C( sp3) Bond Formation

被引：49

作者：

Zucca, Antonio ^{[1
]}

Maidich, Luca ^{[1
,2
]}

Canu, Laura ^{[1
]}

Petretto, Giacomo L. ^{[1
]}

Stoccoro, Sergio ^{[1
]}

Cinellu, Maria Agostina ^{[1
]}

Clarkson, Guy J. ^{[2
]}

Rourke, Jonathan P. ^{[2
]}

机构：

[1] Univ Sassari, Dipartimento Chim & Farm, I-07100 Sassari, Italy

[2] Univ Warwick, Dept Chem, Coventry CV4 7AL, W Midlands, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 18期

关键词：

bond coupling; NMR spectroscopy; platinum; reductive elimination; rollover cyclometalation; ARYL REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; CRYSTAL-STRUCTURE; GAS-PHASE; H BOND; PLATINUM(II) COMPLEXES; METHYL-IODIDE; CYCLOMETALATION; ACTIVATION; ALKYL;

D O I：

10.1002/chem.201304257

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a rollover/retro-rollover reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR3)] resulted in a rare C(sp(2))C(sp(3)) bond formation to give the bidentate nitrogen ligands 3-methyl-2,2-bipyridine, 3,6-dimethyl-2,2-bipyridine, and 3-methyl-2-(2-pyridyl)-quinoline, which were isolated and characterized. The nature of the phosphane PR3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of CH bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize.

引用

页码：5501 / 5510

页数：10

共 61 条

[1] Carenium-Calkyl bond making and breaking:: Key process in the platinum-mediated Caryl-Calkyl bond formation.: Analogies to organic electrophilic aromatic substitution [J].