Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (5): 1843-1851.DOI: 10.6023/cjoc202212006 Previous Articles     Next Articles

Special Issue: 有机硼化学专辑



孔德亮, 戴闻, 赵怡玲, 陈艺林, 朱红平*()   

  1. 厦门大学化学化工学院 固体表面物理化学国家重点实验室 厦门 361005
  • 收稿日期:2022-12-06 修回日期:2023-02-23 发布日期:2023-03-07
  • 通讯作者: 朱红平
  • 基金资助:
    国家自然科学基金(21972112); 国家自然科学基金(22078274)

Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules

Deliang Kong, Wen Dai, Yiling Zhao, Yilin Chen, Hongping Zhu()   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2022-12-06 Revised:2023-02-23 Published:2023-03-07
  • Contact: Hongping Zhu
  • Supported by:
    National Natural Science Foundation of China(21972112); National Natural Science Foundation of China(22078274)

A new amidinatoborylaminosilylene (L)[(1,5-C8H14)B(1-Ad)N]Si (3, L=PhC(NtBu)2, 1-Ad=C10H15) has been synthesized. The reactions using 3 in combination of similar compounds (L)[(1,5-C8H14)B(2,4,6-Me3C6H2)N]Si (1) and (L)[(1,5-C8H14)B(2,6-iPr2C6H3)N]Si (2) were investigated toward ketone and diketone substrates. When with Ph2CO, no reaction occurred for 3. However 1 and 2 reacted by an oxidative [1+2]-cycloaddition to produce the SiCO-cycles (L)[(1,5-C8H14)B(2,4,6-Me3C6H2)N]SiOC(Ph2) (4) and (L)[(1,5-C8H14)B(2,6-iPr2C6H3)N]SiOC(Ph2) (5), respectively. Reactions of 1~3 with anthrone yielded compounds (L)[(1,5-C8H14)B(R)N]Si(H)OC(C14H9) (R=2,4,6-Me3C6H2 (6), 2,6-iPr2C6H3 (7), 1-Ad (8)), where the oxidative [1+2] cycloaddition followed by an H-migration from the CH2 group of the central C6-ring of anthrone under aromatization was suggested to proceed through. Furthermore, reactions of 1~3 with benzil gave SiC2O2-cycles as (L)[(1,5-C8H14)B(R)N]SiO2C2(Ph)2 (R=2,4,6-Me3C6H2 (9), 2,6-iPr2C6H3 (10), 1-Ad (11)) undergoing oxidative [1+4] cycloaddition. Compounds 3~11 have been characterized by NMR (1H, 13C, 11B, and/or 29Si ) 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.

Key words: functionalized silylene, oxidative cycloaddition reaction, H-migration under aromatization, Si-containing heterocycle