Methyl transfer from methylcobaloxime to (Triphos)Ni(PPh3):: Relevance to the mechanism of acetyl coenzyme A synthase
Methyl transfer from methylcobaloxime to (Triphos)Ni(PPh3):: Relevance to the mechanism of acetyl coenzyme A synthase
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DOI：
10.1021/ja072063o
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发表时间：
2007-08-01
影响因子：
15
通讯作者：
Riordan, Charles G.
中科院分区：
文献类型：
--
作者：
Eckert, Nathan A.;Dougherty, William G.;Riordan, Charles G.
的零价镍络合物，（triphos）镍（PPh3），定量烷基化的甲基钴肟试剂。独立的化学合成证实含镍产物为阳离子[（triphos）NiMe]（+）。这些研究为在乙酰辅酶A合酶（ACS）生物催化过程中使用Ni（0）亲核试剂提供了小分子先例。相应的（triphos）NiCO不是反应的底物，这为甲基随后是CO的有序结合提供了基于化学的基本原理。
The zerovalent nickel complex, (triphos)Ni(PPh3), is quantitatively alkylated by a methylcobaloxime reagent. Independent chemical synthesis confirms the nickel-containing product as the cation, [(triphos)NiMe](+). These studies provide small molecule precedent for a Ni(0) nucleophile during acetyl coenzyme A synthase (ACS) biocatalysis. That the corresponding (triphos)NiCO is not a substrate for the reaction provides a chemical-based rationale for ordered binding of methyl followed by CO.