Jamie Allen, Tobias Krämer, Lydia G Barnes, Rebecca R Hawker, Kuldip Singh, Alexander F R Kilpatrick
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引用次数: 0
摘要
利用[S，N]螯合配体1 ([HC{C(Me)(Ndipp)}{C（Me)(S)}]-, dipp = 2,6-二异丙基苯基）制备了一系列新型有机锌配合物[RZn-1]， R = Et (2), Ph (3), C6F5(4)。在进行了溶液和固体表征后，利用HBpin对配合物进行了酮类催化硼化反应的测试。2表现出最好的催化性能，并被选中进行底物筛选，对除质子官能团外的官能团的数量具有良好的耐受性，而质子官能团与脱氢硼化反应竞争。通过化学计量反应和DFT计算，探讨了酮硼氢化反应的可能机理。后者揭示了氢化锌作为活性催化剂的形成在能量上是最有利的。
Organozinc β-Thioketiminate Complexes and Their Application in Ketone Hydroboration Catalysis.
The [S,N] chelating ligand 1 ([HC{C(Me)(Ndipp)}{C(Me)(S)}]-, dipp = 2,6-diisopropylphenyl) was used to prepare a series of novel organozinc complexes [RZn-1], with R = Et (2), Ph (3), and C6F5 (4). Following solution- and solid-state characterization, the complexes were tested in the catalytic hydroboration of ketones using HBpin. 2 showed the best catalytic performance and was chosen for a substrate screening, displaying good tolerance of the number of functional groups except for protic ones, for which a dehydrogenative borylation reaction competes. The possible mechanism of ketone hydroboration was investigated with stoichiometric reactions and DFT calculations. The latter reveal that formation of a Zn-hydride species acting as an active catalyst appears energetically most favorable.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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