Direct kinetic formation of nonanomeric [6.5]-spiroketals in aqueous media

被引：11

作者：

Castagnolo, Daniele ^{[1
]}

Breuer, Irene ^{[1
]}

Pihko, Petri M. ^{[1
]}

机构：

[1] Aalto Univ, Organ Chem Lab, FI-02015 Espoo, Finland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 26期

关键词：

D O I：

10.1021/jo702022u

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The direct kinetic formation of spiroketals from mixed ketal-alcohol precursors under acid catalysis was studied using four differently substituted systems. In all cases, the exclusive formation of the anomeric isomer was observed under equilibrating conditions. However, the formation of the nonanomeric spiroketal isomer was observed if the reaction was performed under kinetic conditions using an appropriately tuned acid. Water had a dramatic accelerating effect on the spiroketalization reactions that were performed in THF, and the highest yields of the nonanomeric products were obtained in aqueous THE The nonanomeric/anomeric product ratio was also strongly affected by the substituents and the stereochemistry of the starting alcohol.

引用

页码：10081 / 10087

页数：7

共 34 条

[1] Nonanomerlc spiroketals in natural products: Structures, sources, and synthetic strategies [J].

Aho, JE ;

Pihko, PM ;

Rissa, TK .

CHEMICAL REVIEWS, 2005, 105 (12) :4406-4440

[2] Enantioselective synthesis and absolute configurations of aculeatins A, B, D, and 6-epi-aculeatin D [J].

Alvarez-Bercedo, Paula ;

Falomir, Eva ;

Carda, Miguel ;

Marco, J. A. .

TETRAHEDRON, 2006, 62 (41) :9641-9649

[3] OXIDATION OF DIOLS WITH ALKALI HYPOCHLORITES CATALYZED BY OXAMMONIUM SALTS UNDER 2-PHASE CONDITIONS [J].

ANELLI, PL ;

BANFI, S ;

MONTANARI, F ;

QUICI, S .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (12) :2970-2972

[4] Biomimetic synthesis of (±)-aculeatin D [J].

Baldwin, JE ;

Adlington, RM ;

Sham, VWW ;

Marquez, R ;

Bulger, PG .

TETRAHEDRON, 2005, 61 (09) :2353-2363

[5] Synthesis of the C16-C28 spiroketal subunit of spongistatin 1 (altohyrtin A): The pyrone approach [J].

Crimmins, MT ;

Katz, JD .

ORGANIC LETTERS, 2000, 2 (07) :957-960

[6] Short synthesis of the 6,6-spiroketal cores of spirofungins A and B [J].

Dias, LC ;

de Oliveira, LG .

ORGANIC LETTERS, 2004, 6 (15) :2587-2590

[7] Abbreviated synthesis of the C3-C14 (substituted 1,7-dioxaspiro[5.5]undec-3-ene) system of okadaic acid [J].

Dounay, AB ;

Forsyth, CJ .

ORGANIC LETTERS, 1999, 1 (03) :451-453

[8] Expedient access to the okadaic acid architecture: A novel synthesis of the C1-C27 domain [J].

Dounay, AB ;

Urbanek, RA ;

Frydrychowski, VA ;

Forsyth, CJ .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (03) :925-938

[9] KINETIC HYDROGEN ISOTOPE EFFECTS IN CONCERTED MECHANISM FOR HYDROLYSIS OF ACETALS, KETALS, AND ORTHO ESTERS [J].

ELIASON, R ;

KREEVOY, MM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (22) :7037-7041

[10] Utility of a chiral 1,3-dioxane template in stereoselective intramolecular Diels-Alder reactions [J].

Evanno, Laurent ;

Deville, Alexandre ;

Dubost, Lionel ;

Chiaroni, Angele ;

Bodo, Bernard ;

Nay, Bastien .

TETRAHEDRON LETTERS, 2007, 48 (16) :2893-2896

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