期刊
ORGANIC CHEMISTRY FRONTIERS
卷 3, 期 4, 页码 423-433出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6qo00002a
关键词
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资金
- Chinese National Natural Science Foundation [21375113, 21232005, 21103142, 21573179, 21133007]
- National Basic Research Program of China [2012CB821600, 2013CB910700, 2011CB808504]
- Program for New Century Excellent Talents in University [NCET-13-0511]
- Fundamental Research Funds for the Central Universities [2012121021]
- Program for Changjiang Scholars and Innovative Research Team in University [IRT1263]
Density functional theory (DFT) calculations were carried out to investigate the hydridic character of several main group hydrides. A P-hydrido-1,3,2-diazaphospholene 1f with two pi-electron donor amino groups on the heterocyclic skeleton framework performs as a strong hydride donor owing to the significant n(N) sigma*(P-H) hyperconjugation. The natural bond orbital analysis reveals that high p-electron delocalization exists in both 1f and the corresponding stable phosphenium E-f(+). In addition, 1f is calculated to have a similar catalytic ability for the hydroboration of acetone with pinacolborane, compared to 1e. Thus, a variety of organic substrates activated by 1f are explored, including ketone, imine, isocyanate, CO2, diazene, alkene, alkyne and epoxide. The results show that the highly polarized and electron-deficient bonds such as C=O pi bonds are readily activated, whereas 1f seems difficult to react with electron-rich unsaturated bonds of propene and propyne. More importantly, 1,3,2-diazaphospholene-based compounds, featuring an extremely polarized P-X bond (X = C CMe, NMe2, PMe2 and SMe), are predicted to have a useful catalytic ability. The preliminary computational results suggest that these P-X compounds could catalyze the silylamination, silylphosphination and silylsulfenylation of acetone with TMSNMe2, TMSPMe2 and TMSSMe, respectively. The products are silylethers, which are equivalent to the corresponding alcohols since they easily undergo hydrolysis. Our computational study opens a new avenue to the design of novel main group organocatalysts.
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