Divergent Asymmetric Total Synthesis of (+)-Vincadifformine, (-)-Quebrachamine, (+)-Aspidospermidine, (-)-Aspidospermine, (-)-Pyrifolidine, and Related Natural Products

被引：61

作者：

Wang, Nengzhong ^{[1
]}

Du, Shuo ^{[1
]}

Li, Dong ^{[1
]}

Jiang, Xuefeng ^{[1
,2
]}

机构：

[1] East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, 3663 North Zhongshan Rd, Shanghai 200062, Peoples R China

[2] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China

来源：

ORGANIC LETTERS | 2017年 / 19卷 / 12期

关键词：

BIOMIMETIC ALKALOID SYNTHESES; INTRAMOLECULAR SCHMIDT REACTION; QUATERNARY CARBON CENTERS; FORMAL TOTAL SYNTHESIS; ASPIDOSPERMA ALKALOIDS; INDOLE ALKALOIDS; GENERAL ENTRY; ENANTIOSELECTIVE SYNTHESES; DIHYDROINDOLE ALKALOIDS; REDUCTIVE CYCLIZATION;

D O I：

10.1021/acs.orglett.7b01292

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A uniformly strategic total synthesis of Aspidosperma alkaloids (+)-vincadifformine, (-)-quebrachamine, (+)-aspidospermidine, (-)-aspidospermine, (-)-pyrifolidline, and nine others from efficiently constructed tricyclic ketone 13 is reported. Highlights of these divefgent and practical syntheses include (i) stereoselective intermolecular [4 + 2] Cydoaddition to establish C-E ring with one all-carbon quaternary stereocenter (C-E) and two bridged contiguous cis-stereocenters (C-12 and C-19), (ii) a Pd/C-catalyzed hydrogenation/deprotection/amidation cascade process to assemble the D ring, and (iii) Fischer indolization to forge the A-B ring.

引用

页码：3167 / 3170

页数：4

共 86 条

[1] Enantioselective synthesis of 3,3-disubstituted piperidine derivatives by enolate dialkylation of phenylglycinol-derived oxazolopiperidone lactams [J].

Amat, Mercedes ;

Lozano, Oscar ;

Escolano, Carmen ;

Molins, Elies ;

Bosch, Joan .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (12) :4431-4439

[2] NOVEL PHOTO-ISOMERIZATION OF 1-ACYLINDOLES TO 3-ACYLINDOLENINES - GENERAL ENTRY TO THE TOTAL SYNTHESIS OF STRYCHNOS AND ASPIDOSPERMA ALKALOIDS [J].

BAN, Y ;

YOSHIDA, K ;

GOTO, J ;

OISHI, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (23) :6990-6992

[3] Tandem radical decarboxylation-oxidation of amino acids:: A mild and efficient method for the generation of N-acyliminium ions and their nucleophilic trapping [J].

Boto, A ;

Hernández, R ;

Suárez, E .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (16) :4930-4937

[4]

CAMERMAN A, 1965, TETRAHEDRON LETT, P637

[5] Formal Synthesis of (+)-Kopsihainanine A and Synthetic Study toward (+)-Limaspermidine [J].

Chen, Zhuang ;

Zhou, Shiqiang ;

Jia, Yanxing .

JOURNAL OF ORGANIC CHEMISTRY, 2015, 80 (24) :12545-12551

[6] Diels-Alder cycloadditions of 3,5-dibromo-2-pyrone: A new ambident diene [J].

Cho, CG ;

Kim, YW ;

Lim, YK ;

Park, JS ;

Lee, H ;

Koo, S .

JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (01) :290-293

[7] Total Synthesis of (±)-Aspidospermidine Starting from 3-Ethyl-5-bromo-2-pyrone [J].

Cho, Hyun-Kyu ;

Tam, Nguyen Thanh ;

Cho, Cheon-Gyu .

BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2010, 31 (11) :3382-3384

[8] Highly efficient synthesis of tricyclic Amines by a cyclization/cycloaddition cascade: Total syntheses of aspidospermine, aspidospermidine, and quebrachamine [J].

Coldham, Iain ;

Burrell, Adam J. M. ;

White, Laura E. ;

Adams, Harry ;

Oram, Niall .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (32) :6159-6162

[9] Catalytic Selective Cyclizations of Aminocyclopropanes: Formal Synthesis of Aspidospermidine and Total Synthesis of Goniomitine [J].

De Simone, Filippo ;

Gertsch, Juerg ;

Waser, Jerome .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (33) :5767-5770

[10] STEREOCONTROLLED ELABORATION OF QUATERNARY CARBON CENTERS THROUGH THE ASYMMETRIC MICHAEL REACTION USING CHIRAL IMINES - ENANTIOSELECTIVE SYNTHESIS OF (+)-ASIDOSPERMIDINE [J].

DESMAELE, D ;

DANGELO, J .

JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (09) :2292-2303

← 1 2 3 4 5 6 7 8 9 →