Citation: Wang Qinting, Zhao Shuai, Jin Lei, Chen Xin. Synthesis of Fmoc-protected (S)-3, 5-Dibromophenylalanine in the Presence of a Phase Transfer Catalyst or a Chiral Catalyst[J]. Chinese Journal of Organic Chemistry, ;2016, 36(9): 2242-2246. doi: 10.6023/cjoc201601045 shu

Synthesis of Fmoc-protected (S)-3, 5-Dibromophenylalanine in the Presence of a Phase Transfer Catalyst or a Chiral Catalyst

1.
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164

Corresponding author: Chen Xin, xinchen@cczu.edu.cn
Received Date: 31 January 2016
Revised Date: 17 March 2015

Fund Project: National Natural Science Foundation of China 21272029

Figures(3)

Two methods of catalytic asymmetric synthesis of (S)-3, 5-dibromophenylalanine are presented. One approach is to use asymmetric alkylation reaction starting from diphenylimine glycine tert-butyl ester and 3, 5-dibromobenzyl bromide, with O-allyl-N-9-anthracene methyl bromide cinchonidine as phase-transfer catalyst, the (S)-3, 5-dibromophenylalanine derivative was obtained (up to 94.9% ee). The optimized conditions of asymmetric phase transfer catalytic alkylation are explored. Another method is to employ asymmetric hydrogenation starting from 2-acetylamino-3-(3, 5-dibromophenyl)acrylic acid with bis(1, 5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate and (R)-diphenylphosphino-N-methyl-1-[(S)-2-diphenyl-phos-phino)ferrocenyl]ethylamine[(R)-methyl BoPhoz] as chiral catalyst. (S)-3, 5-Dibromophenylalanine hydrochloride was obtained after hydrolysis. By Fmoc protection, Fmoc-(S)-3, 5-dibromophenylalanine was obtained (up to 94.7% ee). By comparison of the two methods, the first one gives higher overall yield and a little bit better selectivity, and is more suitable for the synthesis of other chiral dihalo-substituented phenylalanine derivatives.
- (S)-3, 5-dibromophenylalanine,
- phase transfer catalyst,
- asymmetric catalytic hydrogenation,
- alkylation
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沈阳化工大学材料科学与工程学院沈阳 110142