Chinese Journal of Organic Chemistry >
Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules
Received date: 2022-12-06
Revised date: 2023-02-23
Online published: 2023-03-07
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.
Deliang Kong , Wen Dai , Yiling Zhao , Yilin Chen , Hongping Zhu . Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules[J]. Chinese Journal of Organic Chemistry, 2023 , 43(5) : 1843 -1851 . DOI: 10.6023/cjoc202212006
| [1] | Sheldrick, W. S. Org. Silicon Compd. 1989, 1, 227. |
| [2] | Cong, S.; Liu, M.; Peng, S.; Zheng, Q.; Li, M.; Guo, Y.; Luo, F. Chin. J. Org. Chem. 2022, 42, 384. (in Chinese) |
| [2] | (从思琪, 刘梦亚, 彭思远, 郑秋翠, 李梦娇, 郭艳, 罗斐贤, 有机化学, 2022, 42, 384.) |
| [3] | Wang, M.; Yu, M.; Wang, W.; Lin, W.; Luo, F. Chin. J. Org. Chem. 2019, 39, 3145. (in Chinese) |
| [3] | (王明凤, 余茂栋, 王文蜀, 林伟立, 罗斐贤, 有机化学, 2019, 39, 3145.) |
| [4] | Qin, X.; Liu, X.; Guo, C.; Wu, H. Chin. J. Org. Chem. 2016, 36, 60. (in Chinese) |
| [4] | (秦晓飞, 刘晓燕, 郭彩红, 武海顺, 有机化学, 2016, 36, 60.) |
| [5] | So, C.-W.; Roesky, H. W.; Magull, J.; Oswald, R. B. Angew. Chem., Int. Ed. 2006, 45, 3948. |
| [6] | Azhakar, R.; Ghadwal, R. S.; Roesky, H. W.; Wolf, H.; Stalke, D. Organometallics 2012, 31, 4588. |
| [7] | So, C.-W.; Roesky, H. W.; Gurubasavaraj, P. M.; Oswald, R. B.; Gamer, M. T.; Jones, P. G.; Blaurock, S. J. Am. Chem. Soc. 2007, 129, 12049. |
| [8] | Yeong, H.-X.; Lau, K.-C.; Xi, H.-W.; Hwa Lim, K.; So, C.-W. Inorg. Chem. 2010, 49, 371. |
| [9] | Azhakar, R.; Roesky, H. W.; Holstein, J. J.; Pr?pper, K.; Dittrich, B. Organometallics 2012, 32, 358. |
| [10] | Breit, N. C.; Szilvási, T.; Inoue, S. Chem. Eur. J. 2014, 20, 9312. |
| [11] | Inoue, S.; Wang, W.; Pra?sang, C.; Asay, M.; Irran, E.; Driess, M. J. Am. Chem. Soc. 2011, 133, 2868. |
| [12] | Azhakar, R.; Pro?pper, K.; Dittrich, B.; Roesky, H. W. Organometallics 2012, 31, 7586. |
| [13] | Breit, N. C.; Eisenhut, C.; Inoue, S. Chem. Commun. 2016, 52, 5523. |
| [14] | Benedek, Z.; Szilvási, T. RSC Adv. 2015, 5, 5077. |
| [15] | Mo, Z.; Szilvási, T.; Zhou, Y.; Yao, S.; Driess, M. Angew. Chem., Int. Ed. 2017, 56, 3699. |
| [16] | Braunschweig, H.; Breckner, T.; Dei?enberger, A.; Dewhurst, R. D.; Gackstatter, A.; G?rtner, A.; Hofmann, A.; Kupfer, A.; Prieschl, D.; Thiess, T.; Wang, S. R. Chem.-Eur. J. 2017, 23, 9491. |
| [17] | Li, J.; Liu, Y.; Kundu, S.; Keil, H.; Zhu, H.; Herbst-Irmer, R.; Stalke, D.; Roesky, H. W. Inorg. Chem. 2020, 59, 7910. |
| [18] | Zhao, Y.; Chen, Y.; Zhang, L.; Li, J.; Peng, Y.; Chen, Z.; Jiang, L.; Zhu, H. Inorg. Chem. 2022, 61, 5215. |
| [19] | Kuczkowski, R. L.; Bryan, P. S. Inorg. Chem. 1971, 10, 200. |
| [20] | Noeth, H.; Staudigl, R.; Wagner, H. U. Inorg. Chem. 1982, 21, 706. |
| [21] | Ghadwal, R. S.; Sen, S. S.; Roesky, H. W.; Granitzka, M.; Kratzert, D.; Merkel, S.; Stalke, D. Angew. Chem., Int. Ed. 2010, 49, 3952. |
| [22] | Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F. Organometallics 1997, 16, 4861. |
| [23] | Ishida, S.; Iwamoto, T.; Kira, M. Organometallics 2010, 29, 5526. |
| [24] | Khoo, S.; Shan, Y.-L.; Yang, M.-C.; Li, Y.; Su, M.-D.; So, C.-W. Inorg. Chem. 2018, 57, 5879. |
| [25] | Tavc?ar, G. P.; Sen, S. S.; Roesky, H. W.; Hey, J.; Kratzert, D.; Stalke, D. Organometallics 2010, 29, 3930. |
| [26] | Asay, M.; Inoue, S.; Driess, M. Angew. Chem., Int. Ed. 2011, 50, 9589. |
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