A Theoretical Investigation of Cycloadditions of Hydrogen Isocyanide to CH2X and PHX Dipolarophiles (X = CH2, NH, O, SiH2, PH, S)
作者:
Minh Tho Nguyen,
Annik Van Keer,
Luc G. Vanquickenborne,
期刊:
Chemische Berichte
(WILEY Available online 1997)
卷期:
Volume 130,
issue 1
页码: 69-76
ISSN:0009-2940
年代: 1997
DOI:10.1002/cber.19971300111
出版商: WILEY‐VCH Verlag
关键词: [2 + 1] Cycloadditions;Hydrogen cyanide;Phosphorus dipolarophiles;Three‐membered rings;Calculations, ab initio
数据来源: WILEY
摘要:
AbstractWe performed a systematic investigation of [2 + 1] cycloadditions of HNC to dipolarophiles of the type CH2X and PHX with XCH2, NH, O, SiH2, PH, and S, as well as HNNH and H2SiSiH2. Ab initio MO calculations at the QCISD(T)/6‐311G(d,p)/MP2/6‐31G(d,p)+ZPE level were applied to construct the minimum‐energy reaction pathways. Calculated results concerning the regiochemistry of the approaches and the stereochemistry of the product formation were analyzed in relation with established concepts such as frontier orbital, net charge distribution and stereoelectronic effect. For some systems, up to four distinct transition structures for cycloaddition were found. In general, there is a certain similarity between the behavior of both C and P series of dipolarophiles. The characteristics of the transition structures can be, in most cases, recovered by using qualitative concepts. The [2 + 1] cycloadditions are highly regioselective and stereospecific. Silicon‐containing dipolarophiles are particularly attractive as they exhibit very small energy barriers to addi
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