Abstract
Conformational isomerism has been studied by ab initio methods (RHF/6-31+G*, MP2/6-31+G*) for CH2=CHCH2X heteroallyl and CH3CH=CHX heteropropenyl systems (X = H, Me, NMe2, OMe, PMe2, SMe, ONCH2). In 3-heteroprop-1-enes, substituents preferably occupy the AC position relative to the C=C double bond. The E isomers of 1-methylthio- and 1-methoxyprop-1-enes, which are thermodynamically more stable, have two stable forms, SP and AC; for 1-dimethylamino- and 1-imethylphosphinoprop-1-enes, the stable forms are AP and SC. The molecule of the E isomer of formoxime propenyl ether exists in two stable rotamer forms, SC and AP, the latter being predominant. The Z isomers preferably exist in the form of AC (X = CH3O, CH3S) and AP (X = (CH3)2N, (CH3)2P, CH2=NO) conformations. Migration of the double bond toward an heteroatom in formoxime allyl ether, forming the E and Z isomers, is energetically favorable, the Z isomer being thermodynamically preferable.
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Kobychev, V.B., Larionova, E.Y. & Klyba, N.S. Ab Initio Study of the Conformational and Geometrical Isomerism in Heteroallyl and Heteropropenyl Systems. Journal of Structural Chemistry 44, 748–756 (2003). https://doi.org/10.1023/B:JORY.0000029810.09191.93
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DOI: https://doi.org/10.1023/B:JORY.0000029810.09191.93