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ID 114028
著者
Chen, Yen-Chou Tokushima University|Hokkaido University
資料タイプ
学術雑誌論文
抄録
Readily available 3-bromopenta-2,4-dienyl esters (1x, acetate; 1y, benzoate; 1z, diethyl phosphate) were applied to the palladium-catalyzed reaction with various soft nucleophiles. The reaction proceeded through the twofold nucleophilic substitution via formal SN2'- and SN2-processes giving the various doubly functionalized allenes 2 in good yields. In the reactions of carboxylates 1x and 1y, the first substitution took place at the C-Br bond to form (allenyl)methyl ester intermediates 3. Because the second substitution on 3 proceeded faster than the first substitution on 1x or 1y, 3 were not isolable and C2-symmetric allenes 2 were obtained even in the presence of remaining 1x and 1y. On the other hand, the phosphate moiety was more reactive than the C-Br moiety in 1z. The initial products from 1z were 5-Nu-3-bromopenta-1,3-dienes 4 which were less reactive than 1z. Monosubstitution products 4 were isolable, and the stepwise introduction of two different Nu groups in C1-symmetric allenes 2 was realized starting with 1z under the controlled reaction conditions. By the use of a chiral palladium catalyst, axially chiral doubly functionalized allenes were obtained in up to 95% ee.
掲載誌名
The Journal of Organic Chemistry
ISSN
00223263
15206904
cat書誌ID
AA00704100
AA12097242
出版者
ACS Publications
84
19
開始ページ
12463
終了ページ
12470
発行日
2019-09-09
権利情報
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.9b01933.
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言語
eng
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著者版
部局
理工学系