Axial coordination of NHC ligands on dirhodium(II) complexes:: Generation of a new family of catalysts

被引：88

作者：

Trindade, Alexandre F. ^{[1
,2
]}

Gois, Pedro M. P. ^{[1
,2
,3
,4
]}

Veiros, Luis F. ^{[1
,2
]}

Andre, Vania ^{[1
,2
]}

Duarte, M. Teresa ^{[1
,2
]}

Afonso, Carlos A. M. ^{[1
,2
]}

Caddick, Stephen ^{[3
]}

Cloke, F. Geoffrey N. ^{[4
]}

机构：

[1] Inst Super Tecn, Dept Engn Quim & Biol, CQFM, P-1049001 Lisbon, Portugal

[2] Inst Super Tecn, Dept Engn Quim & Biol, CQE, P-1049001 Lisbon, Portugal

[3] UCL, Dept Chem, London WC1H 0AJ, England

[4] Univ Sussex, Sch Life Sci, Dept Chem, Brighton BN1 9QJ, E Sussex, England

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2008年 / 73卷 / 11期

关键词：

D O I：

10.1021/jo800087n

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An efficient new methodology for the arylation of aldehydes is disclosed which uses dirhodium(II) catalysts and N-heterocyclic carbene (NHC) ligands. Complexes of Rh-2(OAc)(4) with one and two NHCs attached on the axial positions were successfully isolated, fully characterized, and used as catalysts in the reaction. The saturated monocomplex ((NHC 5)Rh-2(OAc)(4)) 31 was shown to be the most active catalyst and was particularly efficient in the arylation of alkyl aldehydes. DFT calculations support participation of complexes with one axial NHC in the reaction as the catalysts active species and indicate that hydrogen bonds involving dirhodium unit, reactants, and solvent (alcohol) play an important role on the reaction mechanism.

引用

页码：4076 / 4086

页数：11

共 78 条

[11] Efficient aziridination of olefins catalyzed by mixed-valent dirhodium(II,III) caprolactamate [J].

Catino, AJ ;

Nichols, JM ;

Forslund, RE ;

Doyle, MP .

ORGANIC LETTERS, 2005, 7 (13) :2787-2790

[12] Dirhodium(II) caprolactamate: An exceptional catalyst for allylic oxidation [J].

Catino, AJ ;

Forslund, RE ;

Doyle, MP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (42) :13622-13623

[13] The formyl C-H•••O hydrogen bond as a critical factor in enantioselective Lewis-acid catalyzed reactions of aldehydes [J].

Corey, EJ ;

Lee, TW .

CHEMICAL COMMUNICATIONS, 2001, (15) :1321-1329

[14] New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution [J].

Cossi, M ;

Scalmani, G ;

Rega, N ;

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (01) :43-54

[15] Ab initio study of ionic solutions by a polarizable continuum dielectric model [J].

Cossi, M ;

Barone, V ;

Mennucci, B ;

Tomasi, J .

CHEMICAL PHYSICS LETTERS, 1998, 286 (3-4) :253-260

[16] The first dirhodium tetracarboxylate molecule without axial ligation: New insight into the electronic structures of molecules with importance in catalysis and other reactions [J].

Cotton, FA ;

Hillard, EA ;

Murillo, CA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (20) :5658-5660

[17] Catalytic enantioselective C-H activation by means of metal-carbenoid-induced C-H insertion [J].

Davies, HML ;

Beckwith, REJ .

CHEMICAL REVIEWS, 2003, 103 (08) :2861-2903

[18] SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .9. EXTENDED GAUSSIAN-TYPE BASIS FOR MOLECULAR-ORBITAL STUDIES OF ORGANIC MOLECULES [J].

DITCHFIELD, R ;

HEHRE, WJ ;

POPLE, JA .

JOURNAL OF CHEMICAL PHYSICS, 1971, 54 (02) :724-+

[19] Steric and electronic properties of N-heterocyclic carbenes (NHC):: A detailed study on their interaction with Ni(CO)4 [J].

Dorta, R ;

Stevens, ED ;

Scott, NM ;

Costabile, C ;

Cavallo, L ;

Hoff, CD ;

Nolan, SP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (08) :2485-2495

[20]

Doyle M. P., 1998, Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides

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