Oxonia-cope rearrangement and side-chain exchange in the prins cyclization

被引：155

作者：

Crosby, SR

Harding, JR

King, CD

Parker, GD

Willis, CL

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

[2] AstraZeneca UK Ltd, Macclesfield SK10 4TG, Cheshire, England

来源：

ORGANIC LETTERS | 2002年 / 4卷 / 04期

关键词：

D O I：

10.1021/ol0102850

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Evidence is presented here for the mechanism of the Prins cyclization of benzylic homoallylic alcohols, which shows that the outcome of the reaction is dependent upon the substituents on the aromatic ring. The presence of an electron-rich aromatic ring favors an oxonia-Cope rearrangement yielding a symmetrical tetrahydropyran as the major product formed via a side-chain exchange process. In contrast, with electron-deficient aromatic rings the expected 2,4,6-trisubstituted tetrahydropyran is formed.

引用

收藏

页码：577 / 580

页数：4

相关论文

共 26 条

[11] Formation of tetrahydrofuran from homoallylic alcohol via a tandem sequence:: 2-oxonia [3,3]-sigmatropic rearrangement/cyclization catalyzed by In(OTf)3 [J].

Loh, TP ;

Hu, QY ;

Ma, LT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (10) :2450-2451

[12] STUDIES ON THE ROLE OF THE 2-OXONIA COPE REARRANGEMENT IN PI-CYCLIZATIONS OF ALPHA-METHOXYCARBONYL OXYCARBENIUM IONS [J].

LOLKEMA, LDM ;

SEMEYN, C ;

ASHEK, L ;

HIEMSTRA, H ;

SPECKAMP, WN .

TETRAHEDRON, 1994, 50 (24) :7129-7140

[13] Efficient methodology for the construction of substituted spiroketals. Model studies towards the synthesis of the eastern spiroketal subunit of okadaic acid. [J].

Marko, IE ;

Chelle, F .

TETRAHEDRON LETTERS, 1997, 38 (16) :2895-2898

[14] Novel mercuric triflate-catalyzed condensation of ketones and homoallyl alcohols [J].

Nishizawa, M ;

Shigaraki, T ;

Takao, H ;

Imagawa, H ;

Sugihara, A .

TETRAHEDRON LETTERS, 1999, 40 (06) :1153-1156

[15] The first and highly enantioselective crotylation of aldehydes via an allyl-transfer reaction from a chiral crotyl-donor [J].

Nokami, J ;

Ohga, M ;

Nakamoto, H ;

Matsubara, T ;

Hussain, I ;

Kataoka, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (37) :9168-9169

[16] New concept in the allylation of aldehydes: Regiospecific allylation of aldehydes by an allyl-transfer reaction of homoallylic alcohols [J].

Nokami, J ;

Yoshizane, K ;

Matsuura, H ;

Sumida, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (26) :6609-6610

[17]

Roush WR, 2001, SYNLETT, P955

[18] Role of 2-oxonia cope rearrangements in prins cyclization reactions [J].

Rychnovsky, SD ;

Marumoto, S ;

Jaber, JJ .

ORGANIC LETTERS, 2001, 3 (23) :3815-3818

[19] Prins desymmetrization of a C-2-symmetric diol: Application to the synthesis of 17-deoxyroflamycoin [J].

Rychnovsky, SD ;

Yang, G ;

Hu, YQ ;

Khire, UR .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (10) :3022-3023

[20] Segment-coupling prins cyclizations [J].

Rychnovsky, SD ;

Hu, YQ ;

Ellsworth, B .

TETRAHEDRON LETTERS, 1998, 39 (40) :7271-7274