Reversible C-F bond formation and the Au-catalyzed hydrofluorination of alkynes

被引：292

作者：

Akana, Jennifer A. ^{[1
]}

Bhattacharyya, Koyel X. ^{[1
]}

Mueller, Peter ^{[1
]}

Sadighi, Joseph P. ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 25期

关键词：

D O I：

10.1021/ja0723784

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The gold(I) fluoride complex [(SIPr)AuF] [SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] reacts reversibly with 3-hexyne to form a (beta-fluorovinyl)gold(I) species. The more stable fluorovinyl complex trans-{(SIPr)Au[(Ph)CC(F)CH3]}, formed by addition of [(SIPr)AuF] across 1-phenyl-1-propyne, has been characterized crystallographically. Both the protonolysis of a (fluorovinyl)gold complex and the reaction of a cationic (alkyne)gold(I) complex with the mild HF source Et3N center dot 3HF result in fluoroalkene formation. Electrophilic gold(I) complexes, supported by N-heterocyclic carbene ligands and generated in situ, catalyze the trans-hydrofluorination of internal alkynes at room temperature. This catalysis represents a new, selective, and potentially versatile method for the synthesis of fluoroalkenes.

引用

页码：7736 / +

页数：3

共 56 条

[41] Intramolecular hydroarylation of alkynes catalyzed by platinum or gold:: Mechanism and endo selectivity
Nevado, C
Echavarren, AM
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (10) : 3155 - 3164
[42] OLAH GA, 1993, SYNTHESIS-STUTTGART, P693
[43] SYNTHETIC METHODS AND REACTIONS .63. PYRIDINIUM POLY-(HYDROGEN FLUORIDE) (30-PERCENT PYRIDINE 70-PERCENT HYDROGEN-FLUORIDE) - CONVENIENT REAGENT FOR ORGANIC FLUORINATION REACTIONS
OLAH, GA
WELCH, JT
VANKAR, YD
NOJIMA, M
KEREKES, I
OLAH, JA
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1979, 44 (22) : 3872 - 3881
[44] Construction of asymmetric fluorinated carbon centers
Prakash, GKS
Beier, P
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (14) : 2172 - 2174
[45] CHLOROFLUOROACETYLENE AND BROMOFLUOROACETYLENE BY GAS-PHASE DEHALOGENATION OF 1,1-DIFLUOROETHYLENES
RUNGE, A
SANDER, WW
[J]. TETRAHEDRON LETTERS, 1990, 31 (38) : 5453 - 5456
[46] Synthesis of the first gold(I) carbene complex with a gold-oxygen bond first catalytic application of gold(I) complexes bearing N-heterocyclic carbenes
Schneider, SK
Herrmann, WA
Herdtweck, E
[J]. ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2003, 629 (12-13): : 2363 - 2370
[47] Rearrangement of alkynyl sulfoxides catalyzed by gold(I) complexes
Shapiro, Nathan D.
Toste, F. Dean
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (14) : 4160 - +
[48] Modern synthetic methods for fluorine-substituted target molecules
Shimizu, M
Hiyama, T
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (02) : 214 - 231
[49] Teles JH, 1998, ANGEW CHEM INT EDIT, V37, P1415, DOI 10.1002/(SICI)1521-3773(19980605)37:10<1415::AID-ANIE1415>3.0.CO
[50] 2-N

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