Tetrahedron p. 9935 - 9964 (1997)
Update date:2022-07-29
Topics: Cyclopropanation Insertion into C-H Bonds Addition to double bonds Hetero Analogues
Kirmse, Wolfgang
Konrad, Wolfgang
Oezkir, Ismail S.
Phenylcarbenes with -X-CH2Ph and -CH2-X-Ph (X = CH2, O, SiMe2) groups in the ortho position were generated thermally and photolytically from diazo or tosylhydrazone precursors. Stereorandom insertion reactions with β-C-H bonds were observed, pointing to a triplet abstraction-recombination mechanism. Large kinetic and stereochemical deuterium isotope effects support this notion. The ample formation of benzocyclobutenes from 2-CH2-X-Ph substrates is due to insertion of the carbenes into ArCH2-X bonds. Addition to the terminal phenyl groups competes with C-H and C-X insertion. The results of benzophenone sensitization and of trapping with methanol suggest that the intramolecular reactions of functionalized arylcarbenes proceed, at best, competitively with spin inversion.
View MoreYanCheng LongShen Chemical Co.,Ltd.
Contact:+86-515-86668866
Address:No.13,Weiyi Road,Funing Aoyang Industrial Park
Quzhou Ruiyuan chemical Co., Ltd
Contact:+86-570-3039321/3039361/3039308
Address:18# Huayang Road,Quzhou High-tech Industrial Park, Zhejiang China.
Shanghai Pengkai Chemical Co.,Ltd
Contact:+86-21-60526671
Address:No.4226 Duzhuang Rd Minhang District Shanghai China
Contact:+86-717-6370352
Address:168 Chengdong Avenue, Yichang, Hubei 443003, P. R.China
Beijing Century Richap Chemistry Co.,Ltd
Contact:+86- 010-64455497
Address:Guannan County, Lianyungang City, Jiangsu Province, China
Doi:10.1021/ja907184g
(2009)Doi:10.1021/ic102475e
(2011)Doi:10.1055/s-1995-4142
(1995)Doi:10.1016/S0040-4039(01)93835-3
(1989)Doi:10.1002/chir.20898
(2011)Doi:10.1248/cpb.37.3236
(1989)