Abstract
(+/-)-S-adenosyl-DL-(3R*,4S*)-[3,4-2H2]-methionine [a 1:1 mixture of (3R,4S) and (3S,4R)] and (+/-)-S-adenosyl-DL-(3R*,4R*)-[3,4-2H2]methionine [a 1:1 mixture of (3R,4R) and (3S,4S)] were synthesized from (Z)- and (E)-[1,2-2H2]ethene, respectively. Key steps in the synthesis were the antiperiplanar addition of methanesulfenyl chloride to (Z)-[1,2-2H2]ethene, to give a 1:1 mixture of (R,R)- and (S,S)-1-chloro-2-(methylthio)[1,2-2H2)ethane, followed by alkylation with sodium acetamidomalonate and hydrolysis to give an equal mixture of four stereoisomers of [3,4-2H2]methionine [(2R,3R,4S), (2R,3S,4R), (2S,3R,4S), and (2S,3S,4R)]. The other four stereoisomers of [3,4-2H2]methionine were prepared from (E)-(1,2-2H2]ethene. The two sets of stereoisomers of [3,4-2H2]methionine were chemically converted to S-adenosylhomocysteine, methylated to give the corresponding (+/-)-S-adenosyl-DL-methionines, and then incubated with 1-aminocyclopropane-1-carboxylate synthase partially purified from tomato (Lycopersicon esculentum, L.) pericarp tissue. The stereochemistry of the resulting samples of 1-aminocyclopropane-1-carboxylic acid was determined by comparison with the 1H NMR of the chemically synthesized and regio- and stereo-specifically deuterated compound. The results indicate that the hydrogens at the beta carbon of the methionine portion of S-adenosylmethionine do not participate in the reaction and that the ring closure occurs with inversion of configuration at the gamma carbon of the methionine portion of S-adenosyl-methionine, probably through a direct SN2-type displacement of the 5'-methylthio-5'-deoxyadenosine moiety by a carbanion equivalent formed at the alpha carbon of the methionine portion of S-adenosylmethionine.
Full text
PDFSelected References
These references are in PubMed. This may not be the complete list of references from this article.
- Acaster M. A., Kende H. Properties and Partial Purification of 1-Aminocyclopropane-1-carboxylate Synthase. Plant Physiol. 1983 May;72(1):139–145. doi: 10.1104/pp.72.1.139. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Adams D. O., Yang S. F. Ethylene biosynthesis: Identification of 1-aminocyclopropane-1-carboxylic acid as an intermediate in the conversion of methionine to ethylene. Proc Natl Acad Sci U S A. 1979 Jan;76(1):170–174. doi: 10.1073/pnas.76.1.170. [DOI] [PMC free article] [PubMed] [Google Scholar]
- BURROUGHS L. F. 1-Aminocyclopropane-1-carboxylic acid: a new amino-acid in perry pears and cider apples. Nature. 1957 Feb 16;179(4555):360–361. doi: 10.1038/179360a0. [DOI] [PubMed] [Google Scholar]
- Chiang P. K., Cantoni G. L. Activation of methionine for transmethylation. Purification of the S-adenosylmethionine synthetase of bakers' yeast and its separation into two forms. J Biol Chem. 1977 Jul 10;252(13):4506–4513. [PubMed] [Google Scholar]
- Cornforth J. W., Reichard S. A., Talalay P., Carrell H. L., Glusker J. P. Determination of the absolute configuration at the sulfonium center of S-adenosylmethionine. Correlation with the absolute configuration of the diastereomeric S-carboxymethyl-(S)-methionine salts. J Am Chem Soc. 1977 Oct 26;99(22):7292–7300. doi: 10.1021/ja00464a032. [DOI] [PubMed] [Google Scholar]
- Khani-Oskouee S., Jones J. P., Woodard R. W. Stereochemical course of the biosynthesis of 1-aminocyclopropane-1-carboxylic acid. I. Role of the asymmetric sulfonium pole and the alpha-amino acid center. Biochem Biophys Res Commun. 1984 May 31;121(1):181–187. doi: 10.1016/0006-291x(84)90704-6. [DOI] [PubMed] [Google Scholar]
- Kikugawa K., Ichino M. Direct halogenation of sugar moiety of nucleosides. Tetrahedron Lett. 1971 Jan;(2):87–90. doi: 10.1016/s0040-4039(01)96366-x. [DOI] [PubMed] [Google Scholar]
- Lizada M. C., Yang S. F. A simple and sensitive assay for 1-aminocyclopropane-1-carboxylic acid. Anal Biochem. 1979 Nov 15;100(1):140–145. doi: 10.1016/0003-2697(79)90123-4. [DOI] [PubMed] [Google Scholar]
- Yu Y. B., Adams D. O., Yang S. F. 1-Aminocyclopropanecarboxylate synthase, a key enzyme in ethylene biosynthesis. Arch Biochem Biophys. 1979 Nov;198(1):280–286. doi: 10.1016/0003-9861(79)90420-x. [DOI] [PubMed] [Google Scholar]