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Title: A theoretical investigation of cycloadditions of hydrogen isocyanide to CH2=X and PH=X dipolarophiles (X=CH2, NH, O, SiH2, PH, S)
Authors: Nguyen, Minh Tho ×
VanKeer, A
Vanquickenborne, LG #
Issue Date: 1997
Series Title: Chemische Berichte vol:130 issue:1 pages:69-75
Abstract: We performed a systematic investigation of [2 + 1] cycloadditions of HN=C to dipolarophiles of the type CH2=X and PH=X with X= CH2, NH, O, SiH2, PH, and S, as well as HN=NH and H2Si=SiH2. 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 addition to isocyanides.
ISSN: 0009-2940
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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