Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
复制标题
DOI：
10.1002/adsc.202000514
复制
发表时间：
2020-05
影响因子：
5.4
通讯作者：
R. Nolla-Saltiel;Ana M. Geer;Laurence J. Taylor;Olivia Churchill;E. Davies;W. Lewis;A. Blake;D. Kays
中科院分区：
文献类型：
--
作者：
R. Nolla-Saltiel;Ana M. Geer;Laurence J. Taylor;Olivia Churchill;E. Davies;W. Lewis;A. Blake;D. Kays
在此，我们报告了三种含有咔唑烷NNN钳配体的杂配第一行过渡金属(II)配合物的合成，并通过还原羰基化途径转化为相应的金属(I)-羰基配合物。这些配合物是活化烯烃氢膦酸化的预催化剂，提供钴催化的氢膦酸化过程，该过程单独且选择性地产生β加成（反马尔可夫尼科夫）产物。已经使用多种活化烯烃研究了这种转化的范围。底物配位中间体的分离和表征揭示了可用的配位位点，这提供了对所提出的催化循环的深入了解。
Herein we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt-catalysed hydrophosphination process that solely and selectively yields the β addition (anti-Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate-coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle.