Defluorination of heterocyclic ketones: Control of microbasicity

被引:26
作者
Chapman, RD
Welker, MF
Kreutzberger, CB
机构
[1] USN, Air Warfare Weap div, Res & Technol Grp, China Lake, CA 93555 USA
[2] TPL Inc, Albuquerque, NM 87109 USA
关键词
D O I
10.1021/jo9718399
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Difluoramination of a tetrahydro-1,5-diazocine-3,7(2H, 6H)-dione to the corresponding 3,3,7,7-tetrakis(difluoramino)diazocine was achieved by a judicious choice of protecting group. Arenesulfonyl protecting groups for the diazocine nitrogens proved superior to acetyl during the slow disruption of the transannular bridge in 9-oxa-3,7-diazabicyclo[3.3.1]nonane intermediates by difluorosulfamic acid, While a 1,5-ditosyl derivative failed to proceed beyond the product of addition of difluoramine to one ketone carbonyl (hemiaminal 6), the use of 4-nitrobenzenesulfonyl as the protecting groups lowered the nitrogens' basicities below that of the oxygen site in the dione and intermediates, allowing the reaction to proceed to a gem-bis(difluoramino)diazocine product (11). A safer procedure for handling difluoramine is described.
引用
收藏
页码:1566 / 1570
页数:5
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