Reversing the role of the metal-oxygen π-bond.: Chemoselective catalytic reductions with a rhenium(V)-dioxo complex

被引:149
作者
Kennedy-Smith, JJ [1 ]
Nolin, KA [1 ]
Gunterman, HP [1 ]
Toste, FD [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
关键词
D O I
10.1021/ja029498q
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The metal-oxygen bond plays a critical role in some of the most important biological and synthetic reactions. However, the majority of these processes result in the oxidation of the target organic substrate; applications of this class of metal complexes to other organic transformations are extremely rare. In this paper, we report a new type of catalytic process in which complexes with metal-oxygen multiple bonds are used as reductants rather than oxidants. The overall reaction provides a highly chemoselective reduction/protection of carbonyl groups. In addition to providing a new way of catalyzing organic reactions, these catalysts can be used in the presence of a wide range of other functional groups such as amino, cyano, nitro, aryl halo, ester, and alkene; unlike many of their late metal relatives, they are inexpensive as well as air and moisture tolerant. Copyright © 2003 American Chemical Society.
引用
收藏
页码:4056 / 4057
页数:2
相关论文
共 20 条
[1]  
[Anonymous], 1999, HDB REAGENTS ORGANIC
[2]   Chemo- and enantioselective hydrosilylation of carbonyl and imino groups. An emphasis on non-traditional catalyst systems [J].
Carpentier, JF ;
Bette, V .
CURRENT ORGANIC CHEMISTRY, 2002, 6 (10) :913-936
[3]   Catalytic nucleophilic acyl substitution of anhydrides by amphoteric vanadyl triflate [J].
Chen, CT ;
Kuo, JH ;
Li, CH ;
Barhate, NB ;
Hon, SW ;
Li, TW ;
Chao, SD ;
Liu, CC ;
Li, YC ;
Chang, IH ;
Lin, JS ;
Liu, CJ ;
Chou, YC .
ORGANIC LETTERS, 2001, 3 (23) :3729-3732
[4]   RHENIUM(V) OXIDE COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURES OF THE COMPOUNDS TRANS-ETEI2O(OET)(PPH3)2,TRANS-MEEI2O(OME)(PPH3)2 AND OF THEIR HYDROLYSIS DERIVATIVE REIO2(PPH3)2 [J].
CIANI, GF ;
DALFONSO, G ;
ROMITI, PF ;
SIRONI, A ;
FRENI, M .
INORGANICA CHIMICA ACTA-ARTICLES, 1983, 72 (01) :29-37
[5]   Mechanism of dihydrogen cleavage by high-valent metal oxo compounds: Experimental and computational studies [J].
Collman, JP ;
Slaughter, LM ;
Eberspacher, TA ;
Strassner, T ;
Brauman, JI .
INORGANIC CHEMISTRY, 2001, 40 (24) :6272-6280
[6]  
GOUNTCHEV TI, 1997, J AM CHEM SOC, V117
[7]  
Ito H, 2000, SYNLETT, P479
[8]   Synthesis of unsaturated esters from aldehydes: An inexpensive, practical alternative to the Horner-Emmons reaction under neutral conditions [J].
Ledford, BE ;
Carreira, EM .
TETRAHEDRON LETTERS, 1997, 38 (47) :8125-8128
[9]   Synthesis and reactions of rhenium(V) oxo-hydride complexes [J].
Matano, Y ;
Brown, SN ;
Northcutt, TO ;
Mayer, JM .
ORGANOMETALLICS, 1998, 17 (14) :2939-2941
[10]  
Nugent W.A., 1988, METAL LIGAND MULTIPL