Synthesis of spiro-cyclopropane derivatives containing multiple chiral centers  

作　　者：黄慧 陈庆华 

出　　处：《Science China Chemistry》1999年第3期268-276,共9页中国科学（化学英文版）

基　　金：Project supported by the National Natural Science Foundation of China (Grant No. 29672004)

摘　　要：Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2 (5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a–5d which are difficult to obtain by routine methods. The synthetic method for 5a–5d was studied in de-tail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]20, IR,1H NMR,13C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromobutyrolactocyclopropane-3”, 3’ (4’-methyloxy-5’-menthyloxybutyrolactone) ] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.

关 键 词：5-( l-menthyloxy)-3-bromo-2(5H)-furanone tandem reaction asymmetric double Michael addition /internal NUCLEOPHILIC SUBSTITUTION crystal structure spiro-cyclopropane derivatives with MULTIPLE chiral centers. 

分 类 号：O621[理学—有机化学]