Samarium(II)-mediated 4-exo-trig cyclisations of unsaturated aldehydes.: A stereoselective approach to functionalised cyclobutanols

被引：44

作者：

Johnston, D ^{[1
]}

McCusker, CF ^{[1
]}

Muir, K ^{[1
]}

Procter, DJ ^{[1
]}

机构：

[1] Univ Glasgow, Dept Chem, Glasgow G12 8QQ, Lanark, Scotland

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 2000年 / 05期

关键词：

D O I：

10.1039/a909549g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

gamma,delta-Unsaturated aldehydes having a fully substituted centre in either the alpha- or beta-positions, have been prepared from substituted gamma-butyrolactones and undergo efficient 4-exo-trig cyclisation on treatment with samarium(II) iodide to give functionalised cyclobutanols. In all cases cyclisation occurs with complete diastereocontrol to give anti-cyclobutanol products. The stereochemistry of the products has been confirmed by NOE and X-ray crystallographic studies. In the cyclisation of substrates having a third substituent on the double bond, alpha- to the ester, significant control is achieved at the third newly formed stereocentre lying outside the ring. The origin of the stereoselectivity at this third centre and its marked dependence on cosolvent are discussed.

引用

页码：681 / 695

页数：15

共 46 条

[1] Jasonol, a rare tricyclic eudesmane sesquiterpene and six other new sesquiterpenoids from Jasonia candicans [J].

Ahmed, AA ;

Mahmoud, AA .

TETRAHEDRON, 1998, 54 (28) :8141-8152

[2] AN INTRAMOLECULAR COBALT CYCLIZATION FOR THE CONSTRUCTION OF SUBSTITUTED PYRROLIDINES [J].

BALDWIN, JE ;

MOLONEY, MG ;

PARSONS, AF .

TETRAHEDRON, 1992, 48 (42) :9373-9384

[3]

Bernard AM, 1998, SYNLETT, P668

[4] Optically active cyclobutanone chemistry:: Synthesis of (-)-cyclobut-A and (±)-3′-epi-cyclobut-A [J].

Brown, B ;

Hegedus, LS .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (22) :8012-8018

[5] Structure and absolute configuration of protoilludane sesquiterpenes from Russula delica [J].

Clericuzio, M ;

Fu, J ;

Pan, FS ;

Pang, ZJ ;

Sterner, O .

TETRAHEDRON, 1997, 53 (28) :9735-9740

[6] PREPARATION OF 2-(3-BROMO-1-METHYLPROPYL)-1,3-DIOXOLAN AND THE CORRESPONDING CHLORIDE FROM 2-METHYLBUTYROLACTONE [J].

COLLINS, DJ ;

JAMES, AM .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1989, 42 (01) :223-228

[7] Cyclopropane ring formation by an SmI2 mediated cyclisation of δ-halo-α,β-unsaturated esters [J].

David, H ;

Afonso, C ;

Bonin, M ;

Doisneau, G ;

Guillerez, MG ;

Guibé, F .

TETRAHEDRON LETTERS, 1999, 40 (49) :8557-8561

[8] 1,2-STEREOINDUCTION IN RADICALS AND ANIONS - A COMPARISON BETWEEN HYDROGEN ABSTRACTION AND PROTONATION [J].

ERDMANN, P ;

SCHAFER, J ;

SPRINGER, R ;

ZEITZ, HG ;

GIESE, B .

HELVETICA CHIMICA ACTA, 1992, 75 (02) :638-644

[9]

Farrugia L. J., 1999, J. Appl. Crystallogr, V32, P837, DOI [DOI 10.1107/S0021889899006020, 10.1107/S0021889899006020]

[10] Stereoselective Yang cyclizations of α-amido ketones [J].

Griesbeck, AG ;

Heckroth, H ;

Lex, J .

CHEMICAL COMMUNICATIONS, 1999, (12) :1109-1110

← 1 2 3 4 5 →