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Electron transfer photochemistry of 7‐(spirocyclopropane)quadricyclane: capture of a radical cation and sequential cyclopropylcarbinyl rearrangements
Author(s) -
McIlroy Sean,
Weng Hengxin,
Roth Heinz D.
Publication year - 1997
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/(sici)1099-1395(199708)10:8<607::aid-poc931>3.0.co;2-p
Subject(s) - chemistry , adduct , photochemistry , quadricyclane , methanol , cyclopropane , hydrogen atom abstraction , electron transfer , ring (chemistry) , medicinal chemistry , radical , organic chemistry , isomerization , catalysis
Abstract The electron transfer photo‐sensitized reaction of 7‐(spirocyclopropane)quadricyclane ( 1 ) with methanol produces two rearranged mono‐methanol adducts, 2 and 3 , and a bis‐methanol adduct, 4 . The products reveal that 1 ·+ reacts by stereo‐ and regiospecific attack of methanol on one trisubstituted cyclopropane ring. The resulting free radical rapidly undergoes one or two (consecutive) cyclopropylcarbinyl to butenyl rearrangements. The mono‐adducts are formed by net hydrogen abstraction, the di‐adduct via a (secondary) electron transfer reaction of 3 . © 1997 John Wiley & Sons, Ltd.