Net Oxidative Addition of C(sp3)-F Bonds to Iridium via Initial C-H Bond Activation

被引：145

作者：

Choi, Jongwook ^{[1
]}

Wang, David Y. ^{[1
]}

Kundu, Sabuj ^{[1
]}

Choliy, Yuriy ^{[1
]}

Emge, Thomas J. ^{[1
]}

Krogh-Jespersen, Karsten ^{[1
]}

Goldman, Alan S. ^{[1
]}

机构：

[1] Rutgers State Univ, Dept Chem & Chem Biol, New Brunswick, NJ 08903 USA

来源：

SCIENCE | 2011年 / 332卷 / 6037期

关键词：

TRANSITION-METAL-COMPLEXES; REDUCTIVE ELIMINATION; FLUORINE; REACTIVITY; CHEMISTRY; MECHANISM; HYDROGEN;

D O I：

10.1126/science.1200514

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Carbon-fluorine bonds are the strongest known single bonds to carbon and as a consequence can prove very hard to cleave. Alhough vinyl and aryl C-F bonds can undergo oxidative addition to transition metal complexes, this reaction has appeared inoperable with aliphatic substrates. We report the addition of C(sp(3))-F bonds (including alkyl-F) to an iridium center via the initial, reversible cleavage of a C-H bond. These results suggest a distinct strategy for the development of catalysts and promoters to make and break C-F bonds, which are of strong interest in the context of both pharmaceutical and environmental chemistry.

引用

页码：1545 / 1548

页数：4

共 50 条

[41] Catalytic allylic alkylation via the cross-dehydrogenative-coupling reaction between allylic sp3 C-H and methylenic sp3 C-H bonds
Li, ZP
Li, CJ
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (01) : 56 - 57
[42] sp3 C-H Bond Functionalization with Ruthenium Catalysts
Bruneau, Christian
RUTHENIUM IN CATALYSIS, 2014, 48 : 195 - 236
[43] Reactions of phosphine ligands with iridium complexes leading to C(sp3)-H bond activation
Tejel, C
Ciriano, MA
Jiménez, S
Oro, LA
Graiff, C
Tiripicchio, A
ORGANOMETALLICS, 2005, 24 (06) : 1105 - 1111
[44] SELECTIVE SP3 C-H BOND ACTIVATION OF ALKYLAROMATICS PROMOTED BY PLATINUM COMPLEXES
MIYASHITA, A
HOTTA, M
SAIDA, Y
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 473 (1-2) : 353 - 358
[45] Lewis Acid-Catalyzed Conjugate Addition of sp3 C-H Bonds to Methylenemalononitriles
Qian, Bo
Shi, Dengjian
Yang, Lei
Huang, Hanmin
ADVANCED SYNTHESIS & CATALYSIS, 2012, 354 (11-12) : 2146 - 2150
[46] sp3 C-H Bond Activation with Ruthenium(II) Catalysts and C(3)-Alkylation of Cyclic Amines
Sundararaju, Basker
Achard, Mathieu
Sharma, Gangavaram V. M.
Bruneau, Christian
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (27) : 10340 - 10343
[47] Chemoselective Activation of sp3 vs sp2 C-H Bonds with Pd(II)
Curto, John M.
Kozlowski, Marisa C.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (01) : 18 - 21
[48] C(sp3)-H Oxidative Addition at Tantalocene Hydrides
Rehbein, Steven M.
Kania, Matthew J.
Neufeldt, Sharon R.
ORGANOMETALLICS, 2023, 42 (11) : 1179 - 1189
[49] Regioselective functionalization of sp2 and sp3 C-H bonds
Daugulis, Olafs
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2015, 249
[50] Iridium-Catalyzed Hydroarylation via C-H Bond Activation
Nishimura, Takahiro
CHEMICAL RECORD, 2021, 21 (12): : 3532 - 3545

← 1 2 3 4 5 →