Synthesis of 4,5-Diazaspiro[2.3]hexanes and 1,2-Diazaspiro[3.3]heptanes as Hexahydropyridazine Analogues.
Synthesis of 4,5-Diazaspiro[2.3]hexanes and 1,2-Diazaspiro[3.3]heptanes as Hexahydropyridazine Analogues.
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DOI：
10.1021/acs.joc.7b02622
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发表时间：
2018-01
期刊：
影响因子：
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通讯作者：
A. K. Pancholi;Greg P. Iacobini;G. Clarkson;D. Porter;M. Shipman
中科院分区：
文献类型：
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作者：
A. K. Pancholi;Greg P. Iacobini;G. Clarkson;D. Porter;M. Shipman
4，5-二氮杂螺[2.3]己烷是通过在容易获得的3-亚烷基-1，2-二氮杂环丁烷的环外双键上进行二卤代卡宾加成而制备的。使用从TMSCF 3/NaI产生的二氟卡宾，通过在烯烃上的立体定向加成，以高达97%的产率产生这些螺环。较低的产率（高达64%），观察到使用更具反应性的二氯卡宾，由于竞争性的插入到N-N键的卡宾。通过3-亚烷基-1，2-二氮杂环丁烷与四氰基乙烯（TCNE）的[2 + 2]环加成反应，以高达99%的产率合成了较大的1，2-二氮杂螺[3.3]庚烷。
4,5-Diazaspiro[2.3]hexanes are made by dihalocarbene addition across the exocyclic double bond of readily accessible 3-alkylidene-1,2-diazetidines. Using difluorocarbene, generated from TMSCF3/NaI, these spirocycles were produced in yields up to 97% by stereospecific addition across the alkene. Lower yields (up to 64%) were observed using more reactive dichlorocarbene, due to competitive insertion of the carbene into the N-N bond. Larger 1,2-diazaspiro[3.3]heptanes are produced by [2 + 2] cycloaddition of 3-alkylidene-1,2-diazetidines with tetracyanoethylene (TCNE) in up to 99% yield.