Enantiospecific Total Synthesis of the Hapalindoles, Fischerindoles, and Welwitindolinones via a Redox Economic Approach

被引：240

作者：

Richter, Jeremy M. ^{[1
]}

Ishihara, Yoshihiro ^{[1
]}

Masuda, Takeshi ^{[1
]}

Whitefield, Brandon W. ^{[1
]}

Llamas, Tomas ^{[1
]}

Pohjakallio, Antti ^{[1
]}

Baran, Phil S. ^{[1
]}

机构：

[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 52期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1021/ja806981k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Full details are provided for the total synthesis of several members of the hapalindole family of natural products, including hapalindole Q, 12-epi-hapalindole D, 12-epi-fischerindole U, 12-epi-fischerindole G, 12-epi-fischerindole 1, and welwitindolinone A. Use of the recently developed direct indole coupling enabled an efficient, practical, scalable, and protecting-group-free synthesis of each of these natural products. The original biosynthetic proposal is reviewed, and a revised biosynthetic hypothesis is suggested, validated by the above syntheses. The syntheses are also characterized by an adherence to the concept of "redox economy". Analogous to "atom economy" or "step economy", "redox economy" minimizes the superfluous redox manipulations within a synthesis; rather, the oxidation state of intermediates linearly and steadily increases throughout the course of the synthesis.

引用

页码：17938 / 17954

页数：17

共 106 条

[31] Aryllead(IV) reagents in synthesis:: Formation of the C11 quaternary center of N-methylwelwitindolinone C isothiocyanate [J].

Deng, HB ;

Konopelski, JP .

ORGANIC LETTERS, 2001, 3 (19) :3001-3004

[32] ACTION OF TERT-BUTYL AZIDOFORMATE ON THE CONJUGATE BASES OF 1,2,3,4-TETRAHYDRO-9H-CARBAZOLE AND OTHER INDOLE-DERIVATIVES [J].

DHANAK, D ;

NEIDLE, S ;

REESE, CB .

TETRAHEDRON LETTERS, 1985, 26 (16) :2017-2020

[33] Inhibition of bacterial RNA polymerase by the cyanobacterial metabolites 12-epi-hapalindole E isonitrile and calothrixin A [J].

Doan, NT ;

Stewart, PR ;

Smith, GD .

FEMS MICROBIOLOGY LETTERS, 2001, 196 (02) :135-139

[34]

Doan NT, 2000, J APPL PHYCOL, V12, P409

[35] ALLYLIC SULFOXIDES - USEFUL INTERMEDIATES IN ORGANIC SYNTHESIS [J].

EVANS, DA ;

ANDREWS, GC .

ACCOUNTS OF CHEMICAL RESEARCH, 1974, 7 (05) :147-155

[36] DIMERIZATION OF A 3-SUBSTITUTED OXINDOLE AT C-3 AND ITS APPLICATION TO THE SYNTHESIS OF (+/-)-FOLICANTHINE [J].

FANG, CL ;

HORNE, S ;

TAYLOR, N ;

RODRIGO, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (21) :9480-9486

[37] LITHIUM AND POTASSIUM TRIALKYLBOROHYDRIDES - REAGENTS FOR DIRECT REDUCTION OF ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS TO SYNTHETICALLY VERSATILE ENOLATE ANIONS [J].

FORTUNATO, JM ;

GANEM, B .

JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (12) :2194-2200

[38] Indol-2-one intermediates:: Mechanistic evidence and synthetic utility.: Total syntheses of (±)-flustramines A and C [J].

Fuchs, JR ;

Funk, RL .

ORGANIC LETTERS, 2005, 7 (04) :677-680

[39] STEREOCONTROLLED SYNTHESIS OF (-)-HAPALINDOLE-G [J].

FUKUYAMA, T ;

CHEN, XQ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (07) :3125-3126

[40]

GORTHEY LA, 1985, J ORG CHEM, V50, P4173

← 1 2 3 4 5 6 7 8 9 10 →