Chiral C2-boron-bis(oxazolines) in asymmetric catalysis -: A theoretical study of the catalyzed enantioselective reduction of ketones promoted by catecholborane

被引：15

作者：

Bandini, Marco ^{[1
]}

Bottoni, Andrea ^{[1
]}

Cozzi, Pier Giorgio ^{[1
]}

Miscione, Gian Pietro ^{[1
]}

Monari, Magda ^{[1
]}

Pierciaccante, Rossana ^{[1
]}

Umani-Ronchi, Achille ^{[1
]}

机构：

[1] Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2006年 / 2006卷 / 20期

关键词：

ab initio calculations; reaction mechanism; asymmetric catalysis; reduction; boron-bis(oxazolines);

D O I：

10.1002/ejoc.200600133

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

C-2-Symmetrical boron complexes, prepared by the reactions of 2,2'-methylenebis(oxazolines) (BOXs) with catecholborane (CATBH), can be used as catalysts (5-10 mol-%) in the enantioselective reduction of prochiral ketones (ee 72-86%), giving the desired alcohols in satisfactory yields. We have theoretically investigated the mechanism of the reduction of chloroacetophenone at the DFT level and the computational results have provided a complete mechanistic picture, which explains the stereochemical outcome of the reaction. The B-BOXate complex binds both the reducing agent CATBH and the carbonyl compound, activating the former as a hydride donor and enhancing the electrophilicity of the latter. Moreover, the structure of two boron-BOX (BOXate) complexes has been confirmed by means of X-ray diffraction techniques. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

引用

页码：4596 / 4608

页数：13

共 73 条

[1] Quantum mechanical study of stereoselectivity in the oxazaborolidine-catalyzed reduction of acetophenone [J].

Alagona, G ;

Ghio, C ;

Persico, M ;

Tomasi, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (33) :10027-10039

[2] SIR97:: a new tool for crystal structure determination and refinement [J].

Altomare, A ;

Burla, MC ;

Camalli, M ;

Cascarano, GL ;

Giacovazzo, C ;

Guagliardi, A ;

Moliterni, AGG ;

Polidori, G ;

Spagna, R .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 :115-119

[3] Poly(ethylene glycol)-supported bisoxazolines as ligands for catalytic enantioselective synthesis [J].

Annunziata, R ;

Benaglia, M ;

Cinquini, M ;

Cozzi, F ;

Pitillo, M .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (09) :3160-3166

[4] A new catalytic enantioselective approach to optically active lactones by addition reactions to α-dicarbonyl compounds [J].

Audrain, H ;

Jorgensen, KA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (46) :11543-11544

[5] Bis(oxazoline)titanium complexes as chiral catalysts for enantioselective hydrosilylation of ketones - A combined experimental and theoretical investigation [J].

Bandini, M ;

Bernardi, F ;

Bottoni, A ;

Cozzi, PG ;

Miscione, GP ;

Umani-Ronchi, A .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 2003 (15) :2972-2984

[6] Enantioselective reduction of ketones with triethoxysilane catalyzed by chiral bis-oxazoline titanium complexes [J].

Bandini, M ;

Cozzi, PG ;

Negro, L ;

Umani-Ronchi, A .

CHEMICAL COMMUNICATIONS, 1999, (01) :39-40

[7] Design of boron bis-oxazolinate (B-BOXate) complexes: a new class of stable organometallic catalysts [J].

Bandini, M ;

Cozzi, PG ;

Monari, M ;

Perciaccante, R ;

Selva, S ;

Umani-Ronchi, A .

CHEMICAL COMMUNICATIONS, 2001, (14) :1318-1319

[8] Zinc triflate-bis-oxazoline complexes as chiral catalysts:: enantioselective reduction of α-alkoxy-ketones with catecholborane [J].

Bandini, M ;

Cozzi, PG ;

de Angelis, M ;

Umani-Ronchi, A .

TETRAHEDRON LETTERS, 2000, 41 (10) :1601-1605

[9] CHIRALITY AND THE METAL-ALKENE BOND - DISTORTIONS IN THE SOLUTION AND SOLID-STATE STRUCTURES OF ETA(2)-ETHENE RHODIUM BIS-OXAZOLINYLMETHANE COMPLEXES [J].

BROWN, JM ;

GUIRY, PJ ;

PRICE, DW ;

HURSTHOUSE, MB ;

KARALULOV, S .

TETRAHEDRON-ASYMMETRY, 1994, 5 (04) :561-564

[10]

*BRUK AN XRAY INST, 1998, SMART SAINT SOFTW RE

← 1 2 3 4 5 6 7 8 →