Journal of the American Chemical Society p. 1074 - 1080 (1992)
Update date:2022-08-03
Topics:
Guengerich, F. Peter
Raney, Veronica M.
The etheno derivatives of nucleic acid bases contain an additional ring and are of interest because of their useful fluorescence properties and their potential as mutagenic lesions in DNA. The mechanism of formation from 2-haloacetaldehydes is known to involve initial Schiff base formation at an exocyclic nitrogen; however, mechanisms of formation from the more relevant 1-substituted oxiranes have not been established. The reaction of N6-methyladenosine (5) with 1-chlorooxirane yielded the stable carbinolamine 7,8-dihydro-8-hydroxy-9-methyl-3-β-D-ribofuranosylimidazo[2,1-i]purinium species (10), consistent with initial attack of the N1 atom of adenine at the methylene of 1-chlorooxirane. No products indicative of initial reaction at the N6 atom of adenine were found. Reaction of 2,2-dibromoethanol with adenosine or cytidine at pH 9.2 yielded 1,N6-ethenoadenosine (1) or 3,N4-ethenocytidine (2), respectively, presumably via the base-catalyzed formation of 1-bromooxirane from the bromohydrin. When reactions were done with 2,2-dibromo[1-13C]ethanol, 1 contained label only at C-7 and 2 contained label only at C-3. A role for 2-bromoacetaldehyde in these reactions was ruled out by the lack of incorporation of deuterium from 2H2O into 1 under conditions where the exchange of the methylene protons of 2-bromoacetaldehyde with the solvent was relatively rapid. The collective results are most consistent with a mechanism in which the basic endocyclic nitrogen (N1 of adenine or N3 of cytosine) reacts with the methylene carbon of the 1-halooxirane, and, after ring opening and loss of the leaving group, the resulting aldehyde reacts with the exocyclic nitrogen to form the additional ring.
View MoreLaizhou City Laiyu Chemical CO.,Ltd
Contact:+86-535-2719337/2719339
Address:Chenggang road zhuyou laizhou City Shangdong China
Xiamen Kaijia Imp & Exp Co., Ltd.
Contact:86-592-5101177
Address:Room406 Luhui Building No. 65 Haitian Road Huli Xiamen,China.
Hubei Lansun Biochemical Pharmaceutical Co., Ltd
Contact:714-6395977
Address:No. 81 Pengcheng Avenue, economic and technological development zone, Huangshi City, Hubei Province,China
Shanghai Xinda Pharmaceuticals Co., Ltd.
Contact:86-21-33692333-8008
Address:999 Linxian Road, Jinshan Industrial Park, Shanghai, China
Jiacheng-Chem Enterprises Limited(expird)
Contact:86-571-86711508
Address:19 Floor, CIBC Holley International Building, No. 198,Wuxing Road, Hangzhou, China,310020
Doi:10.1021/ol0101281
(2001)Doi:10.1016/S0020-1693(01)00441-8
(2001)Doi:10.1021/om971049p
(1998)Doi:10.1021/ja00752a078
(1971)Doi:10.1016/S0008-6215(00)88026-X
(1972)Doi:10.1039/P19720001225
(1972)