α-Fluoroalkylation of carbonyl compounds mediated by a highly reactive alkyl-rhodium complex

被引：19

作者：

Sato, Kazuyuki ^{[1
]}

Yamazoe, Satoshi ^{[1
]}

Akashi, Yukiko ^{[1
]}

Hamano, Tetsuya ^{[1
]}

Miyamoto, Arisa ^{[1
]}

Sugiyama, Shuhei ^{[1
]}

Tarui, Atsushi ^{[1
]}

Omote, Masaaki ^{[1
]}

Kumadaki, Itsumaro ^{[1
]}

Ando, Akira ^{[1
]}

机构：

[1] Setsunan Univ, Fac Pharmaceut Sci, Osaka 5730101, Japan

来源：

JOURNAL OF FLUORINE CHEMISTRY | 2010年 / 131卷 / 01期

关键词：

alpha-Fluoroalkylation; Rhodium; Silyl enol ether; alpha-Position; SILYL ENOL ETHERS; RADICAL TRIFLUOROMETHYLATION; PERFLUOROALKYL IODIDES; DIASTEREOSELECTIVE TRIFLUOROMETHYLATION; ORGANOFLUORINE COMPOUNDS; FLUORINATING AGENTS; TITANIUM ATE; TRIETHYLBORANE; KETONES; ACETALS;

D O I：

10.1016/j.jfluchem.2009.10.012

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Treatment of silyl enol ethers of various carbonyl compounds with Et2Zn and fluoroalkyl halides (R-f-X) in the presence of RhCl(PPh3)(3) in DME gave the corresponding alpha-R-f carbonyl corn pounds. A highly reactive alkyl-rhodium complex Which was derived from RhCl(PPh3)(3) and Et2Zn must be crucial in this reaction by accelerating the reaction rate and improving the yields dramatically. This reaction overcomes difficulties on the synthesis of alpha-R-f carbonyl compounds due to inverse polarization of R-f-X. (C) 2009 Elsevier B.V. All rights reserved.

引用

页码：86 / 90

页数：5

共 31 条

[1]

Bgu J.-P., 2008, Bioorganic and Medicinal Chemistry of Fluorine

[2]

Cantacuz?ne D., 1975, TETRAHEDRON LETT, V16, P2031

[3] CONDENSATION OF PERFLUOROALKYL IODIDES WITH UNSATURATED NITROGEN-COMPOUNDS [J].

CANTACUZENE, D ;

WAKSELMAN, C ;

DORME, R .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1977, (12) :1365-1371

[4] ELECTRONEGATIVITY OF GROUPS [J].

HUHEEY, JE .

JOURNAL OF PHYSICAL CHEMISTRY, 1965, 69 (10) :3284-&

[5] DIASTEREOSELECTIVE TRIFLUOROMETHYLATION OF CHIRAL IMIDE ENOLATES WITH IODOTRIFLUOROMETHANE MEDIATED BY TRIETHYLBORANE [J].

ISEKI, K ;

NAGAI, T ;

KOBAYASHI, Y .

TETRAHEDRON LETTERS, 1993, 34 (13) :2169-2170

[6] DIASTEREOSELECTIVE TRIFLUOROMETHYLATION OF CHIRAL IMIDE ENOLATES WITH IODOTRIFLUOROMETHANE MEDIATED BY TRIETHYLBORANE [J].

ISEKI, K ;

NAGAI, T ;

KOBAYASHI, Y .

TETRAHEDRON-ASYMMETRY, 1994, 5 (06) :961-974

[7] Facile radical trifluoromethylation of lithium enolates [J].

Itoh, Y ;

Mikami, K .

ORGANIC LETTERS, 2005, 7 (22) :4883-4885

[8] Radical trifluoromethylation of titanium ate enolate [J].

Itoh, Y ;

Mikami, K .

ORGANIC LETTERS, 2005, 7 (04) :649-651

[9] Experimental and theoretical studies on radical trifluoromethylation of titanium ate and lithium enolates [J].

Itoh, Yoshimitsu ;

Houk, K. N. ;

Mikami, Koichi .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (23) :8918-8925

[10] Radical trifluoromethylation of ketone Li enolates [J].

Itoh, Yoshimitsu ;

Mikami, Koichi .

TETRAHEDRON, 2006, 62 (30) :7199-7203

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