Reactions of Hydrido(hydrosilylene)tungsten Complexes with α,β-Unsaturated Carbonyl Compounds: Selective Formation of (η3-Siloxyallyl)tungsten Complexes
Reactions of Hydrido(hydrosilylene)tungsten Complexes with α,β-Unsaturated Carbonyl Compounds: Selective Formation of (η3-Siloxyallyl)tungsten Complexes
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DOI：
10.1021/ja074629e
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发表时间：
2007-08
影响因子：
15
通讯作者：
Takahito Watanabe;H. Hashimoto;H. Tobita
中科院分区：
文献类型：
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作者：
Takahito Watanabe;H. Hashimoto;H. Tobita
氢基（C5 Me 4 R1）（CO）2（H）WSi（H）[C（SiMe 3）3] [R1 = Me（1a），R1 = Et（1b）]与α，β-不饱和羰基化合物R2 C（O）CHCHR 3反应（R2 = Me，R3 = H或Ph; R_2 = OMe，R_3 = H）在室温下几乎定量地和区域选择性地得到外反（η_3-烯丙基）钨配合物（C_5Me_4R_1）（CO）_2W [η_3-R_3HCCHCR_2 OSiH_2 {C（SiMe_3）_3}]。提出了可能的反应机理，涉及[2+4]环加成过程。
Hydrido(hydrosilylene)tungsten complexes (C5Me4R1)(CO)2(H)WSi(H)[C(SiMe3)3] [R1 = Me (1a), R1 = Et (1b)] reacted with α,β-unsaturated carbonyl compounds R2C(O)CHCHR3 (R2 = Me, R3 = H or Ph; R2 = OMe, R3 = H) at room temperature to give exo-anti (η3-siloxyallyl)tungsten complexes (C5Me4R1)(CO)2W[η3-R3HCCHCR2OSiH2{C(SiMe3)3}] almost quantitatively and regioselectively. Possible reaction mechanisms involving a [2+4] cycloaddition process are proposed.