A highly stereoselective approach to the synthesis of functionalized pyran derivatives by Lewis acid assisted ketal reduction and allylation

被引：10

作者：

Bogaczyk, S ^{[1
]}

Brescia, MR ^{[1
]}

Shimshock, YC ^{[1
]}

DeShong, P ^{[1
]}

机构：

[1] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2001年 / 66卷 / 12期

关键词：

D O I：

10.1021/jo010252y

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reduction of bicyclic ketal 1 gave functionalized pyran derivatives 7a or 7b in a highly stereoselective manner, depending upon the reduction conditions utilized. For example, treatment of ketal 1 with TiCl4/Et3SiH produced exclusively diol 7b with the 2,5-syn relationship in good yield. Alternatively, reduction of ketal 1 by DIBALH gave 2,5-anti-diol 7a stereoselectively. Alane reductions of ketal 1 were highly stereoselective also; however, the syn/anti selectivity observed was strongly dependent an the ratio of reagents employed for in situ generation of the alane. Lewis acid catalyzed allylation of ketal 1 gave pyran 10 in a stereospecific alkylation reaction.

引用

页码：4352 / 4355

页数：4

共 29 条

[1] ASYMMETRIC-SYNTHESIS VIA ACETAL TEMPLATES .3. ON THE STEREOCHEMISTRY OBSERVED IN THE CYCLIZATION OF CHIRAL ACETALS OF POLYOLEFINIC ALDEHYDES - FORMATION OF OPTICALLY-ACTIVE HOMOALLYLIC ALCOHOLS [J].

BARTLETT, PA ;

JOHNSON, WS ;

ELLIOTT, JD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (07) :2088-2089

[2] SELECTIVE REDUCTIONS .X. REACTION OF ALUMINUM HYDRIDE WITH SELECTED ORGANIC COMPOUNDS CONTAINING REPRESENTATIVE FUNCTIONAL GROUPS . COMPARISON OF REDUCING CHARACTERISTICS OF LITHIUM ALUMINUM HYDRIDE AND ITS DERIVATIVES [J].

BROWN, HC ;

YOON, NM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (07) :1464-&

[3] ON THE STEREOSELECTIVE OPENING OF ACHIRAL DIOXANE ACETALS [J].

DENMARK, SE ;

ALMSTEAD, NG .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (22) :6458-6467

[4] STUDIES ON THE MECHANISM AND ORIGIN OF STEREOSELECTIVE OPENING OF CHIRAL DIOXANE ACETALS [J].

DENMARK, SE ;

ALMSTEAD, NG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :8089-8110

[5] TOTAL SYNTHESIS OF (+/-)-TIRANDAMYCIN-A [J].

DESHONG, P ;

RAMESH, S ;

ELANGO, V ;

PEREZ, JJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (18) :5219-5224

[6] ACID-CATALYZED REARRANGEMENT OF PYRAN DERIVATIVES - AN APPROACH TO THE STEREOSELECTIVE SYNTHESIS OF 1,3-DIOL DERIVATIVES [J].

DESHONG, P ;

SIMPSON, DM ;

LIN, MT .

TETRAHEDRON LETTERS, 1989, 30 (22) :2885-2888

[7] TOTAL SYNTHESIS OF THE (+)-PHEROMONE OF THE MALE SWIFT MOTH HEPIALUS-HECTA L [J].

DESHONG, P ;

LIN, MT ;

PEREZ, JJ .

TETRAHEDRON LETTERS, 1986, 27 (19) :2091-2094

[8] MAJOR REDUCING SPECIES OPERATIVE WHEN AN EQUIMOLAR PROPORTION OF ALCL3 IS ADDED OVER A SHORT PERIOD OF TIME TO AN ETHER SOLUTION OF EQUIMOLAR PROPORTIONS OF LIALH4 AND ACETAL OR KETAL [J].

DINER, UE ;

DAVIS, HA ;

BROWN, RK .

CANADIAN JOURNAL OF CHEMISTRY, 1967, 45 (03) :207-&

[9] LANTHANOIDS IN ORGANIC-SYNTHESIS .6. THE REDUCTION OF ALPHA-ENONES BY SODIUM-BOROHYDRIDE IN THE PRESENCE OF LANTHANOID CHLORIDES - SYNTHETIC AND MECHANISTIC ASPECTS [J].

GEMAL, AL ;

LUCHE, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (18) :5454-5459

[10]

GRAY GR, 1992, FRONTIERS CARBOHYDRA, V2, P154

← 1 2 3 →