Aroyl chlorides react with terminal alkynes accompanied by decarbonylation in the presence of a catalytic amount of[RhCl(cod)](2) and PPh(3) to give the corresponding vinyl chloride derivatives regio- and stereoselectively in good yields. The catalyst efficiency is a marked function of the ratio of PPh(3) to the rhodium species; satisfactory results are obtained by employing a PPh(3)/Rh ratio of 1.0. The reaction may involve chlororhodation to the alkynes by the intermediary arylchlororhodium(III) species generated in situ followed by reductive elimination of the products, which are suggested by the results of some control experiments. In contrast to the reaction with terminal alkynes, that with some internal ones proceeds without decarbonylation to produce 2,3-disubstituted-1-indenones as the predominant products. The product structures suggest that, while the arylchlororhodium intermediate is also involved, arylrhodation to the alkynes, reinsertion of CO (coordinated to the metal), and intramolecular cyclization sequentially take place to give the indenones.
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UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
LAROCK, RC
DOTY, MJ
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UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
DOTY, MJ
CACCHI, S
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UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
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ACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINAACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINA
MA, SM
LU, XY
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ACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINAACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINA
机构:
UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
LAROCK, RC
DOTY, MJ
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h-index: 0
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UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
DOTY, MJ
CACCHI, S
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UNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALYUNIV ROMA LA SAPIENZA,DIPARTIMENTO STUDI CHIM & TECNOL SOSTANZE BIOL ATT,ROME,ITALY
机构:
ACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINAACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINA
MA, SM
LU, XY
论文数: 0引用数: 0
h-index: 0
机构:
ACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINAACAD SINICA,SHANGHAI INST ORGAN CHEM,345 LINGLING LU,SHANGHAI 200032,PEOPLES R CHINA