The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

被引：294

作者：

Hong, Allen Y. ^{[1
]}

Stoltz, Brian M. ^{[1
]}

机构：

[1] CALTECH, Warren & Katharine Schlinger Lab Chem & Chem Engn, Div Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2013年 / 2013卷 / 14期

基金：

美国国家卫生研究院;

关键词：

Total synthesis; Asymmetric catalysis; Natural products; Palladium; Allylation; All-carbon quaternary stereocenters; ENANTIOSELECTIVE TOTAL-SYNTHESIS; FORMAL TOTAL-SYNTHESIS; SILYL ENOL ETHERS; CONCISE SYNTHESIS; ALLYLATION; KETONES; ALDEHYDES; LIGANDS; ESTERS; ALPHA;

D O I：

10.1002/ejoc.201201761

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

All-carbon quaternary stereocenters have posed significant challenges in the synthesis of complex natural products. These important structural motifs have inspired the development of broadly applicable palladium-catalyzed asymmetric allylic alkylation reactions of unstabilized non-biased enolates for the synthesis of enantioenriched -quaternary products. This microreview outlines key considerations in the application of palladium-catalyzed asymmetric allylic alkylation reactions and presents recent total syntheses of complex natural products that have employed these powerful transformations for the direct, catalytic, enantioselective construction of all-carbon quaternary stereocenters.

引用

页码：2745 / 2759

页数：15

共 115 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]

Aoyama Y, 2001, SYNLETT, P1452

[3] A Formal Total Synthesis of Platencin [J].

Austin, Kerrie A. B. ;

Banwell, Martin G. ;

Willis, Anthony C. .

ORGANIC LETTERS, 2008, 10 (20) :4465-4468

[4]

Baba S.E., 1994, Bull. Soc. Chim. Fr, V131, P525

[5] The enantioselective Tsuji allylation [J].

Behenna, DC ;

Stoltz, BM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (46) :15044-15045

[6]

Behenna DC, 2012, NAT CHEM, V4, P130, DOI [10.1038/nchem.1222, 10.1038/NCHEM.1222]

[7] Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies [J].

Behenna, Douglas C. ;

Mohr, Justin T. ;

Sherden, Nathaniel H. ;

Marinescu, Smaranda C. ;

Harned, Andrew M. ;

Tani, Kousuke ;

Seto, Masaki ;

Ma, Sandy ;

Novak, Zoltan ;

Krout, Michael R. ;

McFadden, Ryan M. ;

Roizen, Jennifer L. ;

Enquist, John A., Jr. ;

White, David E. ;

Levine, Samantha R. ;

Petrova, Krastina V. ;

Iwashita, Akihiko ;

Virgil, Scott C. ;

Stoltz, Brian M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (50) :14199-14223

[8] Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork-Danheiser approach: preparation of mono-, bi-, and tricyclic systems [J].

Bennett, Nathan B. ;

Hong, Allen Y. ;

Harned, Andrew M. ;

Stoltz, Brian M. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2012, 10 (01) :56-59

[9] Enantioselective total synthesis of (+)- and (-)-nigellamine A2 [J].

Bian, Jianwei ;

Van Wingerden, Matthew ;

Ready, Joseph M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (23) :7428-7429

[10] Stereoselective construction of quaternary stereocenters [J].

Christoffers, J ;

Baro, A .

ADVANCED SYNTHESIS & CATALYSIS, 2005, 347 (11-13) :1473-1482

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