9-Diazofluorene (DAF) is decomposed either stoichiometrically or catalytically in the presence of the platinum(0) complex [Pt(C2H4)(PPh3)(2)] to give difluoren-9-ylidene-hydrazine in high yield. Under analogous reaction conditions, diphenyldiazomethane gives mostly the azine, Ph2C=N-N-CPh2, while ethyl diazoacetate (EDA) affords, in low yield, a mixture of diethyl fumarate and maleate in approximately 10:1 molar ratio. The cyclopropanation of styrene with EDA is catalyzed by a series of dicationic complexes of the type [PtL2(NCCH3)(2)][Y](2) (L-2 = 2PPh(3), Ph2PCH = CHPPh2, Ph2PCH2CH2PPh2: Y = BF4. CF3SO3) in 1,2-dichloroethane at 60 degreesC for 24 h. DAF and EDA undergo insertion reactions into the O-H bond of alcohols ROH (R = Me, Et, t-Bu, CH2CH=CH2, Ph) at 25 degreesC in CH2Cl2-ROH (DAF or EDA-ROH molar ratio 1, 20) in the presence of 1% mol of several dicationic platinum(II) complexes to give the corresponding ethers in excellent yields. (C) 2002 Elsevier Science B.V. All rights reserved.

Catalytic transformations of diazo compounds promoted by platinum(0) and dicationic platinum(II) complexes

BERTANI, ROBERTA;MICHELIN, RINO;MOZZON, MIRTO;
2002

Abstract

9-Diazofluorene (DAF) is decomposed either stoichiometrically or catalytically in the presence of the platinum(0) complex [Pt(C2H4)(PPh3)(2)] to give difluoren-9-ylidene-hydrazine in high yield. Under analogous reaction conditions, diphenyldiazomethane gives mostly the azine, Ph2C=N-N-CPh2, while ethyl diazoacetate (EDA) affords, in low yield, a mixture of diethyl fumarate and maleate in approximately 10:1 molar ratio. The cyclopropanation of styrene with EDA is catalyzed by a series of dicationic complexes of the type [PtL2(NCCH3)(2)][Y](2) (L-2 = 2PPh(3), Ph2PCH = CHPPh2, Ph2PCH2CH2PPh2: Y = BF4. CF3SO3) in 1,2-dichloroethane at 60 degreesC for 24 h. DAF and EDA undergo insertion reactions into the O-H bond of alcohols ROH (R = Me, Et, t-Bu, CH2CH=CH2, Ph) at 25 degreesC in CH2Cl2-ROH (DAF or EDA-ROH molar ratio 1, 20) in the presence of 1% mol of several dicationic platinum(II) complexes to give the corresponding ethers in excellent yields. (C) 2002 Elsevier Science B.V. All rights reserved.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2428996
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