ACTIVATION OF 1-ALKYNES AT TRIPODAL (POLYPHOSPHINE)RHODIUM SYSTEMS - REGIOSELECTIVE SYNTHESIS OF ENOL ESTERS FROM 1-ALKYNES AND CARBOXYLIC-ACIDS CATALYZED BY RHODIUM(I) MONOHYDRIDES

被引：60

作者：

BIANCHINI, C ^{[1
]}

MELI, A ^{[1
]}

PERUZZINI, M ^{[1
]}

ZANOBINI, F ^{[1
]}

BRUNEAU, C ^{[1
]}

DIXNEUF, PH ^{[1
]}

机构：

[1] UNIV RENNES 1,CHIM COORDINAT ORGAN LAB,CNRS,D04UK,URA,CAMPUS BEAULIEU,F-35042 RENNES,FRANCE

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 04期

关键词：

D O I：

10.1021/om00118a040

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Regioselective formation of 2-(benzoyloxy)propene results from the addition of benzoic acid to propyne in the presence of the trigonal-bipyramidal Rh(I) monohydrides [(PPh3)RhH] (1) and [(NP3)RhH] (2, PP3 = P(CH2CH2PPh2)3, NP3 = N(CH2CH2PPh2)3). The reactions are catalytic under relatively mild conditions (catalyst to substrate ratio 1:100, toluene, 100 °C). A detailed experimental study on the reactions of 1 and 2 with carboxylic acids, 1-alkynes, or carboxylic acid/1-alkyne mixtures has allowed us to draw a catalysis cycle involving the 16-electron fragments [(L)Rh]+ as catalysts (L = PP3, NP3). The catalytic behavior of the precursors 1 and 2 has been compared and contrasted with those of the isostructural and isoelectronic derivatives [(L)Rh(C≡CPh)], [(L)RhCl], and [(PP3)RhMe]. The novel vinylphosphonium complex [(Ph2PCH2CH2)2P(CH2CH2PPh2)Rh{C═C(H)Ph}(O2CPh)] has been synthesized and fully characterized by IR and1H and31P{1H} NMR techniques. © 1990, American Chemical Society. All rights reserved.

引用

页码：1155 / 1160

页数：6

共 35 条

[11] UNPRECEDENTED TRANSFORMATION OF A VINYLIDENE LIGAND - SYNTHESIS AND ELECTRON-SPIN-RESONANCE CHARACTERIZATION OF A PARAMAGNETIC SIGMA-ACETYLIDE COMPLEX OF RHODIUM(II) [J].

BIANCHINI, C ;

LASCHI, F ;

OTTAVIANI, F ;

PERUZZINI, M ;

ZANELLO, P .

ORGANOMETALLICS, 1988, 7 (07) :1660-1661

[12] OXIDATIVE ADDITION REDUCTIVE ELIMINATION OF ALDEHYDES AND KETONES AT RHODIUM [J].

BIANCHINI, C ;

MELI, A ;

PERUZZINI, M ;

RAMIREZ, JA ;

VACCA, A ;

VIZZA, F ;

ZANOBINI, F .

ORGANOMETALLICS, 1989, 8 (02) :337-345

[13] ACTIVATION OF 1-ALKYNES AT 16-ELECTRON RHODIUM FRAGMENTS - SOME EXAMPLES OF THERMODYNAMICALLY FAVORED REARRANGEMENTS [M(PI-HC=CR)]-][M(H)(C=CR)] [J].

BIANCHINI, C ;

MASI, D ;

MELI, A ;

PERUZZINI, M ;

RAMIREZ, JA ;

VACCA, A ;

ZANOBINI, F .

ORGANOMETALLICS, 1989, 8 (09) :2179-2189

[14] TRIPODAL POLYPHOSPHINE LIGANDS IN HOMOGENEOUS CATALYSIS .1. HYDROGENATION AND HYDROFORMYLATION OF ALKYNES AND ALKENES ASSISTED BY ORGANORHODIUM COMPLEXES WITH MEC(CH2PPH2)3 [J].

BIANCHINI, C ;

MELI, A ;

PERUZZINI, M ;

VIZZA, F ;

FREDIANI, P ;

RAMIREZ, JA .

ORGANOMETALLICS, 1990, 9 (01) :226-240

[15]

BIANCHINI C, 1988, J CHEM SOC CHEM COMM, P210

[16] ANALYSIS OF NMR SPECTRA BY LEAST SQUARES [J].

CASTELLANO, S ;

BOTHNERB.AA .

JOURNAL OF CHEMICAL PHYSICS, 1964, 41 (12) :3863-+

[17] DELTA-R RING CONTRIBUTIONS TO P-31 NMR PARAMETERS OF TRANSITION-METAL-PHOSPHORUS CHELATE COMPLEXES [J].

GARROU, PE .

CHEMICAL REVIEWS, 1981, 81 (03) :229-266

[18] CHEMISTRY OF CARBANIONS .19. ALKYLATION OF ENOLATES FROM UNSYMMETRICAL KETONES [J].

HOUSE, HO ;

GALL, M ;

OLMSTEAD, HD .

JOURNAL OF ORGANIC CHEMISTRY, 1971, 36 (16) :2361-&

[19]

INOKUCHI T, 1987, CHEM LETT, V28, P1553

[20] ACYLATION .7. KINETICS AND MECHANISM OF ENOL-ACETYLATION OF ACETOPHENONE BY ISOPROPENYL ACETATE CATALYSED BY TOLUENE PARA SULPHONIC ACID [J].

JEFFERY, EA ;

SATCHELL, DP .

JOURNAL OF THE CHEMICAL SOCIETY, 1962, (MAY) :1906-&

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