ALPHA-METHYLENE BETA-LACTONES AS MASKED ALLENES AND ALLENE EQUIVALENTS - SOME SELECTED CHEMICAL-TRANSFORMATIONS

被引:41
作者
ADAM, W [1 ]
ALBERT, R [1 ]
HASEMANN, L [1 ]
SALGADO, VON [1 ]
NESTLER, B [1 ]
PETERS, EM [1 ]
PETERS, K [1 ]
PRECHTL, F [1 ]
VONSCHNERING, HG [1 ]
机构
[1] MAX PLANCK INST FESTKORPERFORSCH,W-7000 STUTTGART,GERMANY
关键词
D O I
10.1021/jo00020a017
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Selective chemical transformations have been performed on a number of alpha-methylene beta-lactones to illustrate that these highly functionalized heterocycles serve as useful building blocks in organic synthesis. Thus, thermal decarboxylation of these ''masked allenes'' provides a useful regioselective preparation of allenes with a predetermined substitution pattern. Nucleophilic addition takes place at the carbonyl group with ring opening, but free-radical addition, e.g., thiophenol, and electrophilic addition, e.g., bromine, proceed at the exomethylene group with preservation of the beta-lactone ring. [4 + 2] Cycloaddition with cyclopentadiene affords the expected beta-lactones, which on thermal decarboxylation lead to 2-alkylidenenorbornenes. This regio- and stereoselective transformation establishes the alpha-methylene beta-lactones as valuable allene equivalents. The alpha-methylene beta-lactones serve also as dipolarophiles by undergoing readily 1,3-dipolar cycloaddition with diazoalkanes. Reaction with Lawesson's reagent affords a hitherto unknown alpha-methylene beta-(S)-lactone.
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页码:5782 / 5785
页数:4
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