Enantioselective Lewis acid catalyzed Michael reactions of alkylidene malonates.: Catalysis by C2-symmetric bis(oxazoline) copper(II) complexes in the synthesis of chiral, differentiated glutarate esters

被引：172

作者：

Evans, DA ^{[1
]}

Rovis, T ^{[1
]}

Kozlowski, MC ^{[1
]}

Downey, CW ^{[1
]}

Tedrow, JS ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2000年 / 122卷 / 38期

关键词：

D O I：

10.1021/ja002246+

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Ct-symmetric bis(oxazorine)-Cu(TT) complexes 1 catalyze the Mukaiyama Michael reaction of alkylidene malonates and enolsilanes The use of hexafluoro-2-propanol is essential to induce catalyst turnover. High enantioselectivities are exhibited by bulky alkylidene malonate beta-substituents using catalyst la. The glutarate ester products are readily decarboxylated to provide chiral 1,5-dicarbonyl synthons. Crystallographic characterization of substrate-catalyst complexes provides insight into the binding event with these catalysts and affords a rationale for the observed facial selectivities.

引用

页码：9134 / 9142

页数：9

共 80 条

[21] Cationic bis(oxazoline) and pyridyl-bis(oxazoline)Cu(II) and Zn(II) Lewis acid catalysts. A comparative study in catalysis of Diels-Alder and aldol reactions [J].

Evans, DA ;

Kozlowski, MC ;

Tedrow, JS .

TETRAHEDRON LETTERS, 1996, 37 (42) :7481-7484

[22] C-2-symmetric copper(II) complexes as chiral Lewis acids. Catalytic enantioselective aldol additions of enolsilanes to pyruvate esters [J].

Evans, DA ;

Kozlowski, MC ;

Burgey, CS ;

MacMillan, DWC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (33) :7893-7894

[23] C2-symmetric copper(II) complexes as chiral Lewis acids.: Scope and mechanism of the catalytic enantioselective aldol additions of enolsilanes to pyruvate esters [J].

Evans, DA ;

Burgey, CS ;

Kozlowski, MC ;

Tregay, SW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (04) :686-699

[24] Bis(oxazoline) and bis(oxazolinyl)pyridine copper complexes as enantioselective Diels-Alder catalysts: Reaction scope and synthetic applications [J].

Evans, DA ;

Barnes, DM ;

Johnson, JS ;

Lectka, R ;

von Matt, P ;

Miller, SJ ;

Murry, JA ;

Norcross, RD ;

Shaughnessy, EA ;

Campos, KR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (33) :7582-7594

[25] Catalytic enantioselective amination of enolsilanes using C2-symmetric copper(II) complexes as chiral Lewis acids [J].

Evans, DA ;

Johnson, DS .

ORGANIC LETTERS, 1999, 1 (04) :595-598

[26] Catalytic enantioselective hetero Diels-Alder reactions of α,β-unsaturated acyl phosphonates with enol ethers [J].

Evans, DA ;

Johnson, JS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (19) :4895-4896

[27] C2-symmetric copper(II) complexes as chiral Lewis acids.: Enantioselective catalysis of the glyoxylate-ene reaction [J].

Evans, DA ;

Burgey, CS ;

Paras, NA ;

Vojkovsky, T ;

Tregay, SW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (23) :5824-5825

[28] An improved procedure for the preparation of 2,2-bis[2-[4(S)-tert-butyl-1,3-oxazolinyl]]propane [(S,S)-tert-butylbis(oxazoline)] and derived copper(II) complexes [J].

Evans, DA ;

Peterson, GS ;

Johnson, JS ;

Barnes, DM ;

Campos, KR ;

Woerpel, KA .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (13) :4541-4544

[29] Reversal in enantioselectivity of tert-butyl versus phenyl-substituted bis(oxazoline)copper(II) catalyzed hetero Diels-Alder and ene reactions.: Crystallographic and mechanistic studies [J].

Evans, DA ;

Johnson, JS ;

Burgey, CS ;

Campos, KR .

TETRAHEDRON LETTERS, 1999, 40 (15) :2879-2882

[30] Cationic bis(oxazoline)Cu(II) Lewis acid catalysts. Enantioselective furan Diels-Alder reaction in the synthesis of ent-shikimic acid [J].

Evans, DA ;

Barnes, DM .

TETRAHEDRON LETTERS, 1997, 38 (01) :57-58

← 1 2 3 4 5 6 7 8 →