摘要
合成了一种新的脒基胺硼基硅宾化合物(L)[(1,5-C_(8)H_(14))B(1-Ad)N]Si(3,L=Ph C(N^(t)Bu)_(2),1-Ad=C_(10)H_(15)),进一步研究了3和另外两种脒基胺硼基硅宾化合物(L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]Si(1)和(L)[(1,5-C_(8)H_(14))B(2,6-^(i)Pr_(2)C_(6)H_(3))N]Si(2)分别与酮类分子的反应.化合物1和2分别与二苯甲酮发生[1+2]氧化环加成反应,生成了Si CO-三元环化合物(L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]SiOC(Ph_(2))(4)和(L)[(1,5-C_(8)H_(14))B(2,6-^(i)Pr_(2)C_(6)H_(3))N]SiOC(Ph_(2))(5),化合物3不发生反应.化合物1~3都能与蒽酮发生[1+2]氧化环加成,并进一步环芳香化以及CH_(2)基团H^(-)迁移,生成硅氢蒽氧化物(L)[(1,5-C_(8)H_(14))B(R)N]Si(H)OC(C_(14)H_(9))[R=2,4,6-Me_(3)C_(6)H_(2)(6),2,6-^(i)Pr_(2)C_(6)H_(3)(7),1-Ad(8)].最后探讨了化合物与二苯二乙酮的反应,经过[1+4]氧化环加成得到Si C_(2)O_(2)-五元环化合物(L)[(1,5-C_(8)H_(14))B(R)N]SiO_(2)C_(2)(Ph)_(2)[R=2,4,6-Me_(3)C_(6)H_(2)(9),2,6-^(i)Pr_(2)C_(6)H_(3)(10),1-Ad(11)].对新合成的化合物3~11进行了核磁共振波谱和元素分析表征,并对化合物3,5~6以及8~10进行了X射线单晶衍射结构测定,探究了这些化合物的结构特征,并讨论了这些反应的机理.
A new amidinatoborylaminosilylene (L)[(1,5-C_(8)H_(14))B(1-Ad)N]Si (3,L=Ph C(Nt Bu)_(2),1-Ad=C_(10)H_(15)) has been synthesized.The reactions using 3 in combination of similar compounds (L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]Si (1) and(L)[(1,5-C_(8)H_(14))B(2,6-^(i)Pr_(2)C_(6)H_(3))N]Si (2) were investigated toward ketone and diketone substrates.When with Ph_(2)CO,no reaction occurred for 3.However 1 and 2 reacted by an oxidative[1+2]-cycloaddition to produce the SiCO-cycles(L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]Si OC(Ph_(2))(4) and (L)[(1,5-C_(8)H_(14))B(2,6-^(i)Pr_(2)C_(6)H_(3))N]SiOC(Ph_(2))(5),respectively.Reactions of 1~3 with anthrone yielded compounds (L)[(1,5-C_(8)H_(14))B(R)N]Si(H)OC(C_(14)H_9)(R=2,4,6-Me_(3)C_(6)H_(2) (6),2,6-^(i)Pr_(2)C_(6)H_(3)(7),1-Ad (8)),where the oxidative[1+2]cycloaddition followed by an H^(-)-migration from the CH_(2) group of the central C_(6)-ring of anthrone under aromatization was suggested to proceed through.Furthermore,reactions of 1~3 with benzil gave SiC_(2)O_(2)-cycles as (L)[(1,5-C_(8)H_(14))B(R)N]SiO_(2)C_(2)(Ph)_(2) (R=2,4,6-Me_(3)C_(6)H_(2) (9),2,6-^(i)Pr_(2)C_(6)H_(3) (10),1-Ad (11)) undergoing oxidative[1+4]cycloaddition.Compounds 3^(1)1 have been characterized by NMR (^(1)H,^(13)C,^(11)B,and/or ^(29)Si) and CHN-elemental analysis,of which 3,5~6,and 8-10 were further illustrated by X-ray crystallography.The molecule structures of these compounds were descibed and the reaction mechanisms were discussed.
作者
孔德亮
戴闻
赵怡玲
陈艺林
朱红平
Kong Deliang;Dai Wen;Zhao Yiling;Chen Yilin;Zhu Hongping(State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005)
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2023年第5期1843-1851,共9页
Chinese Journal of Organic Chemistry
基金
国家自然科学基金(Nos.21972112,22078274)资助项目。
