Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

被引：5

作者：

Sharp, Phillip P. ^{[1
]}

Mikusek, Jiri ^{[1
]}

Ho, Junming ^{[1
,2
]}

Krenske, Elizabeth H. ^{[1
]}

Banwell, Martin G. ^{[1
]}

Coote, Michelle L. ^{[1
,3
]}

Ward, Jas S. ^{[1
]}

Willis, Anthony C. ^{[1
]}

机构：

[1] Australian Natl Univ, Inst Adv Studies, Res Sch Chem, Canberra, ACT 2601, Australia

[2] Univ New South Wales, Sch Chem, Sydney, NSW 2052, Australia

[3] Australian Natl Univ, Res Sch Chem, ARC Ctr Excellence Electromat Sci, Canberra, ACT 2601, Australia

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 22期

基金：

澳大利亚研究理事会;

关键词：

ENOL ETHERS; DICHLOROCARBENE ADDUCTS; BUILDING-BLOCKS; PYRROLES; ROUTE;

D O I：

10.1021/acs.joc.8b01766

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly inter converting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinyl-carbene insertion pathway is less likely to be operative.

引用

页码：13678 / 13690

页数：13

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