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

[51] Promoter-dependent course of the Beckmann rearrangement of stereoisomeric spiro[4.4]nonane-1,6-dione monoximes [J].

Hilmey, DG ;

Paquette, LA .

ORGANIC LETTERS, 2005, 7 (10) :2067-2069

[52] Synthetic studies toward halichlorine: Complex azaspirocycle formation with use of an NBS-promoted semipinacol reaction [J].

Hurley, Paul B. ;

Dake, Gregory R. .

JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (11) :4131-4138

[53] N-bromosuccinimide promoted ring expansion reactions:: Diastereoselective formation of functionalized azaspirocyclic cyclopentanones [J].

Hurley, PB ;

Dake, GR .

SYNLETT, 2003, (14) :2131-2134

[54] A chiral base desymmetrisation-ring- closing metathesis route to chiral azaspirocycles: Synthesis of core structures related to pinnaic acid and halichlorine [J].

Huxford, T ;

Simpkins, NS .

SYNLETT, 2004, (13) :2295-2298

[55]

Ito T, 2001, SYNLETT, P1506

[56] SYNTHESIS AND CHIROPTICAL PROPERTIES OF SOME PIPERIDIN-2-ONES [J].

JACKMAN, LM ;

WEBB, RL ;

YICK, HC .

JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (10) :1824-1831

[57] Synthesis of Four Novel Natural Product Inspired Scaffolds for Drug Discovery [J].

Jenkins, Ian D. ;

Lacrampe, Fabienne ;

Ripper, Justin ;

Alcaraz, Lilian ;

Van Le, Phuc ;

Nikolakopoulos, George ;

Leone, Priscila de Almeida ;

White, Rodney H. ;

Quinn, Ronald J. .

JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (03) :1304-1313

[58] Diastereoselective Synthesis of Cyclopentapyridazinones via Radical Cyclization: Synthetic Studies Toward Halichlorine [J].

Keck, Gary E. ;

Heumann, Stacey A. .

ORGANIC LETTERS, 2008, 10 (21) :4783-4786

[59] Studies on the synthesis of pinnaic acid and halichlorine.: Stereoselective preparation of a (Z)-δ-chloro-γ,δ-unsaturated-β-keto phosphonate as a side chain synthon [J].

Keen, SP ;

Weinreb, SM .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (19) :6739-6741

[60] Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst [J].

Keitz, Benjamin K. ;

Endo, Koji ;

Herbert, Myles B. ;

Grubbs, Robert H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (25) :9686-9688

← 1 2 3 4 5 6 7 8 9 10 →