Coordination and Ring Expansion of 1,2-Dipolar Molecules with 9-Phenyl-9-borafluorene
Coordination and Ring Expansion of 1,2-Dipolar Molecules with 9-Phenyl-9-borafluorene
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DOI：
10.1021/acs.organomet.8b00497
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发表时间：
2018-09-10
期刊：
影响因子：
2.8
通讯作者：
Martin, Caleb D.
中科院分区：
文献类型：
--
作者：
Bluer, Kristen R.;Laperriere, Leif E.;Martin, Caleb D.
研究了9-苯基-9-硼杂芘与一系列1，2-偶极有机分子的反应性，发现既可生成加合物，也可生成七元杂环。腈、亚胺和异腈形成相应的配位络合物，其未显示转化为扩环产物的证据。醛、酮和乙烯酮将C=O部分插入内环B-C键中，产生BOC 5硼杂环。异氰酸酯插入C=N或C=O，这取决于底物的极化，其中前者是产生BNC 5环系统的唯一底物。结果表明，9-硼杂芴作为有效试剂生成具有联苯骨架的七元硼杂环的潜力。
The reactivity of 9-phenyl-9-borafluorene with a series of 1,2-dipolar organic molecules is investigated, revealing that either adducts or seven-membered heterocycles are generated. A nitrile, imine, and isonitrile formed the corresponding coordination complexes that showed no evidence of conversion to ring expanded products. An aldehyde, ketone, and ketene inserted the C=O moiety into the endocyclic B-C bond resulting in BOC5 boracycles. Isocyanates inserted either C=N or C=O depending on the polarization of the substrate with the former being the only substrate to generate a BNC5 ring system. The results demonstrate the potential of 9-borafluorenes as effective reagents to generate seven-membered boracycles with a biphenyl backbone.