Chemoenzymatic Enantioselective Synthesis of the Hancock Alkaloids (S)- and (R)-Galipeine, (S)-Cuspareine, (S)-Galipinine, and (S)-Angustureine

被引:0
作者
da Cruz, Nilton Goncalves [1 ]
de Miranda, Amanda Silva [1 ]
Vieira, Henriete da Silva [1 ]
Kohlhoff, Markus [2 ]
Pereira Mendonca, Joao Guilherme [3 ]
Nogueira Diaz, Marisa Alves [3 ]
Diaz-Munoz, Gaspar [1 ]
机构
[1] Univ Fed Minas Gerais, Dept Chem, BR-31270901 Belo Horizonte, MG, Brazil
[2] Oswaldo Cruz Fdn FIOCRUZ, Rene Rachou Inst, Chem Bioact Nat Prod, BR-30190002 Belo Horizonte, MG, Brazil
[3] Univ Fed Vicosa, Dept Biochem & Mol Biol, BR-36570900 Vicosa, MG, Brazil
来源
SYNTHESIS-STUTTGART | 2023年 / 55卷 / 08期
关键词
Hancock alkaloids; enzymatic kinetic resolution; Candida antarctica lipase; Wittig olefination; (R)-galipeine; ASYMMETRIC HYDROGENATION; TETRAHYDROQUINOLINE ALKALOIDS; HETEROAROMATIC-COMPOUNDS; QUINOLINES; DERIVATIVES; (+)-(S)-ANGUSTUREINE; ANGUSTUREINE; GALIPININE; RESOLUTION; CATALYSTS;
D O I
10.1055/a-1984-9689
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The enantioselective synthesis of the Hancock 1,2,3,4-tet-rahydroquinoline alkaloids (S)-galipeine, (S)-cuspareine, (S)-galipinine, and (S)-angustureine and the nonnatural enantiomer (R)-galipeine is described herein. The target compounds were obtained in five steps from a racemic quinaldinic acid derived alpha-amino ester in overall yields of 21.2% to 37.5%. The synthetic route comprised two key steps: an en-zymatic kinetic resolution to control the C-2 stereocenter, affording (R) -and (S)-alpha-amino esters as key chiral intermediates with 94% and 72% ee, respectively, and Wittig olefination of (R)-and (S)-alpha-amino aldehyde synthons with the corresponding phosphonium salts using a phase-transfer system (t-BuOH/CH2Cl2), thereby allowing the introduction of alkyl substituents at C-2. Finally, the enantioselective synthesis was concluded with the catalytic hydrogenation of olefinic bonds on the Wittig adducts to furnish the target Hancock alkaloids, including (R)-galipeine, whose synthesis is described here for the first time.
引用
收藏
页码:1198 / 1206
页数:9
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