NOVEL PALLADIUM-CATALYZED CARBONYLATION OF ORGANIC HALIDES BY CHLOROFORM AND ALKALI
NOVEL PALLADIUM-CATALYZED CARBONYLATION OF ORGANIC HALIDES BY CHLOROFORM AND ALKALI
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DOI：
10.1021/om00034a016
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发表时间：
1993-10-01
期刊：
影响因子：
2.8
通讯作者：
ALPER, H
中科院分区：
文献类型：
--
作者：
GRUSHIN, VV;ALPER, H
在叔膦-钯络合物（1-5摩尔%）的存在下，氯仿和碱水原位生成CO催化羰基化芳烃、乙烯基卤化物和苯基卤化物。羰基化反应在室温下N2下进行，得到相应的羧酸，分离产率高达92%。在相同条件下，苯二苯甲醚催化还原偶联得到1:4的顺式和反式二苯乙烯混合物。用(CHCl3)-C-13标记实验表明，羰基化反应中C1单元的来源是氯仿。钌、铑和钯的三苯基膦配合物催化氯仿的碱性水解生成一氧化碳。以氯仿为催化剂，在KOH存在下合成了羰基配合物[(Ph3P)2Rh(CO)Cl]。
Aromatic, vinylio, and benzylic halides were catalytically carbonylated by CO generated in situ from chloroform and aqueous alkali, in the presence of tertiary phosphine-palladium complexes (1-5 mol %). The carbonylation occurred at ambient temperature under N2, affording the corresponding carboxylic acids in up to 92% isolated yield. Under the same conditions, benzal bromide underwent catalytic reductive coupling to a 1:4 mixture of cis- and trans-stilbenes. A labeling experiment with (CHCl3)-C-13 showed that the source of the C1 unit in the carbonylation is chloroform. Triphenylphosphine complexes of ruthenium, rhodium, and palladium were found to catalyze the alkaline hydrolysis of chloroform to carbon monoxide. A carbonyl complex, [(Ph3P)2Rh(CO)Cl], was synthesized by treatment of Wilkinson's catalyst with chloroform in the presence of KOH.