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Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited
Author(s) -
Moss Robert A.,
Zheng Fengmei,
Johnson Lauren A.,
Sauers Ronald R.
Publication year - 2001
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.371
Subject(s) - chemistry , fragmentation (computing) , ion , computational chemistry , medicinal chemistry , organic chemistry , computer science , operating system
Fragmentations of cyclobutoxychlorocarbene ( 13 , k frag = 7.1 × 10 5 s −1 ) and cyclopropylmethoxychlorocarbene ( 14 , k frag = 7.6 × 10 5 s −1 ) in MeCN proceed to tight and distinct [R + OC Cl − ] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides. B3LYP/6–31G* calculations support these conclusions, affording computed fragmentation activation energies of 6.4 ( 13 ) and 3.0 ( 14 ) kcal mol −1 . Copyright © 2001 John Wiley & Sons, Ltd.