There are no files associated with this item.
Full metadata record
DC Field | Value | Language |
---|---|---|
dc.citation.endPage | 787 | - |
dc.citation.number | 5 | - |
dc.citation.startPage | 781 | - |
dc.citation.title | ORGANIC PROCESS RESEARCH & DEVELOPMENT | - |
dc.citation.volume | 8 | - |
dc.contributor.author | Noh, Hyun Kuk | - |
dc.contributor.author | Lee, Jae Sung | - |
dc.contributor.author | Kim, Yeongdae | - |
dc.contributor.author | Hwang, Gyohyun | - |
dc.contributor.author | Chang, Jay Hyok | - |
dc.contributor.author | Shin, Hyunik | - |
dc.contributor.author | Nam, Do Hyun | - |
dc.contributor.author | Lee, Kyung Hee | - |
dc.date.accessioned | 2023-12-22T10:43:01Z | - |
dc.date.available | 2023-12-22T10:43:01Z | - |
dc.date.created | 2015-07-29 | - |
dc.date.issued | 2004-09 | - |
dc.description.abstract | A novel synthetic route was devised for 4-aminomethyl-3-Z-methoxyiminopyrrolidine methanesulfonate (AMPM), the key intermediate of gemifloxacin, based on chemoselective hydrogenation of the cyano group in 4-cyano-3-methoxyimino-1-(N-tert-butoxycarbonyl)pyrrolidine (CMBP) with minimum reduction lof the methyloxime group employing (t-Boc)(2)O (BOC) as in situ protecting agent. Over Raney nickel or cobalt catalysts, without in situ BOC protection of amine, the side reaction to 4-aminomethyl-3-amino-1-(N-tert-butoxycarbonyl)pyrrolidine (AABP) was extensive by simultaneous hydrogenation of the methyloxime and cyano groups in CMBP, resulting in overreduction of the desired intermediate, 4-aminomethyl-3-Z-methoxyimino 1-(N-tert-butoxycarbonyl)pyrrolidine (Z-AMBP) all the way to AABP. When in situ BOC protection was performed, the selectivity to the desired 4-(N-tert-butoxycarbonyl)aminomethyl-3-Z-methoxyimino-1-(N-tert-butoxycarbon- yl)pyrrolidine (Z-BAMBP) rose to as high as 91% over Raney cobalt by suppressing the over-reduction of Z-AMBP to AABP. On the basis of these observations, a CMBP hydrogenation process over Raney cobalt was proposed. Among noble metal catalysts, only Pd was found to show a high activity. Over Pd catalyst, 4-eyano-3-amino-1-(N-tert-butoxycarbonyl)-3,4-pyrroline (CABP) was found to be a major byproduct, while the formation of AABP or 4-(N-tert-butoxycarbonyl)aminomethyl-3-(N-tert-butoxycarbonyl)amino-1-(N-tert-butoxycarbonyl)pyrrolidine (BABABP) was greatly suppressed. The byproduct CABP formed by hydrogenolysis of the methyl group in the methyloxime group in CMBP could be recycled to the original substrate, 1-(N-tert-butoxycarbonyl)-4-cyano-pyrrolidine-3-one (BCPO) by an acid-catalyzed hydrolysis | - |
dc.identifier.bibliographicCitation | ORGANIC PROCESS RESEARCH & DEVELOPMENT, v.8, no.5, pp.781 - 787 | - |
dc.identifier.doi | 10.1021/op049913u | - |
dc.identifier.issn | 1083-6160 | - |
dc.identifier.scopusid | 2-s2.0-5144222634 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/13106 | - |
dc.identifier.url | http://pubs.acs.org/doi/abs/10.1021/op049913u | - |
dc.identifier.wosid | 000223954700011 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title.alternative | Synthesis of the intermediate of gemifloxacin by the chemoselective hydrogenation of 4-cyano-3-methoxyimino-1-(N-tert-butoxycarbonyl)pyrroidine. Part 1. Screening of metal catalysts | - |
dc.title | Synthesis of the intermediate of gemifloxacin by the chemoselective hydrogenation of 4-cyano-3-methoxyimino-1-(N-tert-butoxycarbonyl)pyrroidine. Part 1. Screening of metal catalysts | - |
dc.type | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
Items in Repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Tel : 052-217-1404 / Email : scholarworks@unist.ac.kr
Copyright (c) 2023 by UNIST LIBRARY. All rights reserved.
ScholarWorks@UNIST was established as an OAK Project for the National Library of Korea.