The Hancock Alkaloids (-)-Cuspareine, (-)-Galipinine, (-)-Galipeine, and (-)-Angustureine: Asymmetric Syntheses and Corrected 1H and 13C NMR Data

被引:30
作者
Davies, Stephen G. [1 ]
Fletcher, Ai M. [1 ]
Houlsby, Ian T. T. [1 ]
Roberts, Paul M. [1 ]
Thomson, James E. [1 ]
Zimmer, David [1 ]
机构
[1] Univ Oxford, Chem Res Lab, Dept Chem, Mansfield Rd, Oxford OX1 3TA, England
来源
JOURNAL OF NATURAL PRODUCTS | 2018年 / 81卷 / 12期
关键词
ENANTIOSELECTIVE TOTAL-SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; ABSOLUTE-CONFIGURATION; CONJUGATE ADDITION; TETRAHYDROQUINOLINES; DERIVATIVES; ACID; HYDROGENATION; QUINOLINES; KETONES;
D O I
10.1021/acs.jnatprod.8b00672
中图分类号
Q94 [植物学];
学科分类号
071001 ;
摘要
The asymmetric syntheses of all members of the Hancock alkaloid family based upon a 2-substituted N-methyl-1,2,3,4-tetrahydroquinoline core are delineated. The conjugate addition of enantiopure lithium N-benzyl-N-(alpha-methyl-p-methoxybenzyl)amide to 5-(o-bromophenyl)-N-methoxy-N-methylpent-2-enamide is used to generate the requisite C-2 stereogenic center of the targets, while an intramolecular Buchwald-Hartwig coupling is used to form the 1,2,3,4-tetrahydroquinoline ring. Late-stage diversification completes construction of the C-2 side chains. Thus, (-)-cuspareine, (-)-galipinine, (-)-galipeine, and (-)-angustureine were prepared in overall yields of 30%, 28%, 15%, and 39%, respectively, in nine steps from commercially available 3-(o-bromophenyl)propanoic acid in all cases. Unambiguously corrected H-1 and C-13 NMR data for the originally isolated samples of (-)-cuspareine, (-)-galipinine, and (-)-angustureine are also reported, representing a valuable reference resource for these popular synthetic targets.
引用
收藏
页码:2731 / 2742
页数:12
相关论文
共 49 条
[1]   Stereoselective Synthesis of Indoline, Tetrahydroquinoline, and Tetrahydrobenzazepine Derivatives from o-Bromophenyl N-tert-Butylsulfinyl Aldimines [J].
Alberto Sirvent, Juan ;
Foubelo, Francisco ;
Yus, Miguel .
JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (03) :1356-1367
[2]   Conjugate Addition of Lithium N-Phenyl-N-(α-methylbenzyl)amide: Application to the Asymmetric Synthesis of (R)-(-)-Angustureine [J].
Bentley, Scott A. ;
Davies, Stephen G. ;
Lee, James A. ;
Roberts, Paul M. ;
Thomson, James E. .
ORGANIC LETTERS, 2011, 13 (10) :2544-2547
[3]   Rearrangement of 4,5-epoxy-9-trimethylsilyldecalines.: Application to the synthesis of the natural eremophilane (-)-aristolochene [J].
Blay, Gonzalo ;
Cardona, Luz ;
Collado, Ana M. ;
Garcia, Begona ;
Pedro, Jose R. .
JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (13) :4929-4936
[4]   Enantiospecific Synthesis of (-)-Cuspareine and (-)-Galipinine [J].
Chacko, Shibin ;
Ramapanicker, Ramesh .
JOURNAL OF HETEROCYCLIC CHEMISTRY, 2015, 52 (06) :1902-1906
[5]   Selective Catalytic Hydrogenation of Heteroarenes with N-Graphene-Modified Cobalt Nanoparticles (Co3O4 Co/NGr@α-Al2O3) [J].
Chen, Feng ;
Surkus, Annette-Enrica ;
He, Lin ;
Pohl, Marga-Martina ;
Radnik, Jorg ;
Topf, Christoph ;
Junge, Kathrin ;
Beller, Matthias .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (36) :11718-11724
[6]   ORIGINS OF THE HIGH STEREOSELECTIVITY IN THE CONJUGATE ADDITION OF LITHIUM(ALPHA-METHYLBENZYL)BENZYLAMIDE TO T-BUTYL CINNAMATE [J].
COSTELLO, JF ;
DAVIES, SG ;
ICHIHARA, O .
TETRAHEDRON-ASYMMETRY, 1994, 5 (10) :1999-2008
[7]   C2-Alkenylation of N-heteroaromatic compounds via Bronsted acid catalysis [J].
Crisenza, Giacomo E. M. ;
Dauncey, Elizabeth M. ;
Bower, John F. .
ORGANIC & BIOMOLECULAR CHEMISTRY, 2016, 14 (24) :5820-5825
[8]   A NEW SYNTHESIS OF N-PROTECTED ALPHA-AMINOMETHYL KETONES FROM GLYCINE [J].
DAVIES, DT ;
OHANLON, PJ .
SYNTHETIC COMMUNICATIONS, 1988, 18 (18) :2273-2280
[9]   Structural Revision of the Hancock Alkaloid (-)-Galipeine [J].
Davies, Stephen G. ;
Fletcher, Ai M. ;
Houlsby, Ian T. T. ;
Roberts, Paul M. ;
Thomson, James E. .
JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (19) :10673-10679
[10]   (-)-Pseudodistomin E: First Asymmetric Synthesis and Absolute Configuration Assignment [J].
Davies, Stephen G. ;
Fletcher, Ai M. ;
Roberts, Paul M. ;
Thomson, James E. ;
Zimmer, David .
ORGANIC LETTERS, 2017, 19 (07) :1638-1641