Enantioselective Total Synthesis of Pinnaic Acid and Halichlorine

被引：29

作者：

Xu, Shu ^{[1
]}

Unabara, Daisuke ^{[1
]}

Uemura, Daisuke ^{[2
]}

Arimoto, Hirokazu ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Life Sci, Sendai, Miyagi 9808577, Japan

[2] Kanagawa Univ, Dept Chem, Fac Sci, Hiratsuka, Kanagawa 2591293, Japan

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2014年 / 9卷 / 01期

关键词：

cyclization; metathesis; natural products; stereoselectivity; total synthesis; COMBINING 2-DIRECTIONAL SYNTHESIS; SPIROCYCLIC CORE; TRICYCLIC CORE; ASYMMETRIC CONSTRUCTION; AZASPIROCYCLIC CORE; RADICAL CYCLIZATION; CLOSING METATHESIS; (+/-)-PINNAIC ACID; FORMAL SYNTHESIS; TANDEM REACTIONS;

D O I：

10.1002/asia.201301248

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The enantioselective total synthesis of the bioactive marine natural products pinnaic acid and halichlorine is reported in detail. Our total synthesis features the construction of the five-membered ring and C9 and C13 stereogenic centers through a palladium-catalyzed trimethylenemethane [3+2] cyclization; the installation of the nitrogen atom through a regioselective Beckmann rearrangement of a poorly reactive ketone; the stereoselective cyclization of the spiro ring through a four-step, one-pot hydrogenation-cyclization; and efficient connection of the sterically hindered lower chain through a reduced-pressure cross olefin metathesis reaction.

引用

页码：367 / 375

页数：9

共 119 条

[1] Iminium ion cascade reactions: stereoselective synthesis of quinolizidines and indolizidines [J].

Amorde, Shawn M. ;

Jewett, Ivan T. ;

Martin, Stephen F. .

TETRAHEDRON, 2009, 65 (16) :3222-3231

[2] Formal syntheses of (+/-)-pinnaic acid and (+/-)-halichlorine [J].

Andrade, RB ;

Martin, SF .

ORGANIC LETTERS, 2005, 7 (25) :5733-5735

[3]

[Anonymous], 1999, ANGEW CHEM

[4] Absolute stereochemistry of halichlorine; A potent inhibitor of VCAM-1 induction [J].

Arimoto, H ;

Hayakawa, I ;

Kuramoto, M ;

Uemura, D .

TETRAHEDRON LETTERS, 1998, 39 (08) :861-862

[5] Synthesis of pinnaic acid; Asymmetric construction of spirocyclic core [J].

Arimoto, H ;

Asano, S ;

Uemura, D .

TETRAHEDRON LETTERS, 1999, 40 (18) :3583-3586

[6] Combining two-directional synthesis and tandem reactions. Part 4: A concise approach to the spirocyclic core of halichlorine and the pinnaic acids [J].

Arini, LG ;

Szeto, P ;

Hughes, DL ;

Stockman, RA .

TETRAHEDRON LETTERS, 2004, 45 (45) :8371-8374

[7] Cyclization via carbolithiation of α-amino alkyllithium reagents [J].

Bahde, Robert J. ;

Rychnovsky, Scott D. .

ORGANIC LETTERS, 2008, 10 (18) :4017-4020

[8] THE SYNTHESIS OF A PRECURSOR TO PENTALENENE USING A PALLADIUM(0) CATALYZED (3+2) CYCLO-ADDITION [J].

BAKER, R ;

KEEN, RB .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1985, 285 (1-3) :419-427

[9] SYNTHESIS OF OPTICALLY-ACTIVE METHYLCYCLOPENTANOIDS - INTERMEDIATES FOR THE ASSEMBLY OF COMPLEX DITERPENOIDS [J].

BECICKA, BT ;

KOERWITZ, FL ;

DRTINA, GJ ;

BAENZIGER, NC ;

WIEMER, DF .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (21) :5613-5619

[10] New approaches to olefin cross-metathesis [J].

Blackwell, HE ;

O'Leary, DJ ;

Chatterjee, AK ;

Washenfelder, RA ;

Bussmann, DA ;

Grubbs, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (01) :58-71

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