Allene substitution-controlled switching of dimerization to cycloisomerization in the PdII-catalyzed reaction of terminal α-allenones

被引：42

作者：

Alcaide, Benito ^{[1
]}

Almendros, Pedro

Martinez del Campo, Teresa

机构：

[1] Univ Complutense Madrid, Fac Quim, Dept Quim Organ 1, E-28040 Madrid, Spain

[2] CSIC, Inst Quim Organ Gen, Consejo Super Invest Cientificas, E-28006 Madrid, Spain

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 2007卷 / 17期

关键词：

allenes; cyclization; heterocycles; palladium; substituent effects; 5-MEMBERED RING-SYSTEMS; FURANS; KETONES; 4-OXOAZETIDINE-2-CARBALDEHYDES; EFFICIENT; LACTAMS; ACCESS;

D O I：

10.1002/ejoc.200700128

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In this contribution, we describe the role of steric interactions in Pd-II-catalyzed reactions of terminal alpha-allenones, which has not previously been invoked in discussions of these versatile compounds. By adopting [PdCl2(MeCN)(2)] as catalyst, the cycloisomerization/dimerization ratio of a-allenones is controlled by the substitution of the allene compound: unsubstituted allenones mainly afford dimerization, whereas allenones bearing an internal substituent favor the formation of cycloisomerization products. Thus, for the first time the mode of reaction (cycloisomerization vs. dimerization) of alpha-allenones is substrate - directable. ((c) Wiley-VCH Verlag GmbH & Co.

引用

页码：2844 / 2849

页数：6

共 47 条

[1] Efficient entry to diversely functionalized spirocyclic oxindoles from isatins through carbonyl-addition/cyclization reaction sequences [J].

Alcaide, B ;

Almendros, P ;

Rodríguez-Acebes, R .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (06) :2346-2351

[2] A practical ruthenium-catalyzed cleavage of the allyl protecting group in amides, lactams, imides, and congeners [J].

Alcaide, B ;

Almendros, P ;

Alonso, JM .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (10) :2874-2879

[3] Synthesis of strained tricyclic β-lactams by intramolecular [2+2] cycloaddition reactions of 2-azetidinone-tethered enallenols:: Control of regioselectivity by selective alkene substitution [J].

Alcaide, B ;

Almendros, P ;

Aragoncillo, C ;

Redondo, MC ;

Torres, MR .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (05) :1539-1546

[4] The allenic Pauson-Khand reaction in synthesis [J].

Alcaide, B ;

Almendros, P .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2004, 2004 (16) :3377-3383

[5] Stereoselective synthesis of 1,2,3-trisubstituted 1,3-dienes through novel [3,3]-sigmatropic rearrangements in α-allenic methanesulfonates:: Application to the preparation of fused tricyclic systems by tandem rearrangement/Diels-Alder reaction [J].

Alcaide, B ;

Almendros, P ;

Aragoncillo, C ;

Redondo, MC .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2005, 2005 (01) :98-106

[6]

Alcaide B, 2002, CHEM-EUR J, V8, P1719, DOI 10.1002/1521-3765(20020402)8:7<1719::AID-CHEM1719>3.0.CO

[7]

2-U

[8] Reaction of two different α-allenols in a heterocyclization/cross-coupling sequence:: Convenient access to functionalized buta-1,3-dienyl dihydrofurans [J].

Alcaide, Benito ;

Almendros, Pedro ;

Martinez del Campo, Teresa .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (27) :4501-4504

[9] Proline-catalyzed diastereoselective direct aldol reaction between 4-oxoazetidine-2-carbaldehydes and ketones [J].

Alcaide, Benito ;

Almendros, Pedro ;

Luna, Amparo ;

Torres, M. Rosario .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (13) :4818-4822

[10] Domino metal-free allene-β-lactam-based access to functionalized pyrroles [J].

Alcaide, Benito ;

Almendros, Pedro ;

Redondo, Maria C. .

CHEMICAL COMMUNICATIONS, 2006, (24) :2616-2618

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