Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

doi:10.6023/cjoc202107062

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (4): 1146-1162.DOI: 10.6023/cjoc202107062 Previous Articles Next Articles

ARTICLES

碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物

王玉斌^a, 郭成^b, 陶晟^a, 刘纪昌^a^,^c, 赵基钢^a^,^c, 刘宁^a^,^*(), 代斌^a^,^*()

a 石河子大学化学化工学院新疆兵团绿色化工过程重点实验室新疆石河子 832003
b 浙江大学医学院第二附属医院癌症研究所杭州 310009
c 华东理工大学化学工程学院上海 200237

收稿日期:2021-07-29 修回日期:2021-09-29 发布日期:2022-05-10
通讯作者: 刘宁, 代斌
基金资助:
兵团中青年科技创新领军人才计划项目(2020CB027); 石河子市中青年科技创新领军人才计划项目(2019RC01); 石河子大学大型贵重仪器设备共享测试基金资助项目.

Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

Yubin Wang^a, Cheng Guo^b, Sheng Tao^a, Jichang Liu^a^,^c, Jigang Zhao^a^,^c, Ning Liu^a(), Bin Dai^a()

a Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003
b Cancer Institute, The Second Affiliated Hospital Zhejiang University School of Medicine, Hangzhou 310009
c School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237

Received:2021-07-29 Revised:2021-09-29 Published:2022-05-10
Contact: Ning Liu, Bin Dai
Supported by:
Xinjiang Bingtuan Young and Middle-Aged Leading Scientists Program(2020CB027); Shihezi Young and Middle-Aged Leading Scientists Program(2019RC01); Open Sharing Fund for the Large-scale Instruments and Equipment of Shihezi University.

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Abstract

A base-controlled strategy for the selective preparation of benzimidazolone and pyrido-benzodiazepine derivatives was developed. The N-alkyl-N-(2-(pyridin-2-ylamino)phenyl)formamides underwent selective coupling to synthesize a series of benzimidazolones when NaOAc was used as bases and employed K₂S₂O₈ as oxidants. By changing bases to NaHCO₃, a series of benzodiazepines was obtained. The possible reaction mechanism was proposed based on the radical-trapping experiments. The applicability of this protocol is demonstrated by scale-up experiments and the functionalization of benzodiazepine products.

Key words: benzimidazolone, benzodiazepine, oxidant-induced, metal-free

Cite this article

Yubin Wang, Cheng Guo, Sheng Tao, Jichang Liu, Jigang Zhao, Ning Liu, Bin Dai. Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1146-1162.

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References 36

[1]	(a) Poupaert, J.; Carato, P.; Colacino, E. Curr. Med. Chem. 2005, 12, 877. pmid: 19788239
	(b) Welsch, M. E.; Snyder, S. A.; Stockwell, B. R. Curr. Opin. Chem. Biol. 2010, 14, 347. doi: 10.1016/j.cbpa.2010.02.018 pmid: 19788239
	(c) Lo, H. Y.; Nemoto, P. A.; Kim, J. M.; Hao, M.-H.; Qian, K. C.; Farrow, N. A.; Albaugh, D. R.; Fowler, D. M.; Schneiderman, R. D.; Michael August, E.; Martin, L.; Hill-Drzewi, M.; Pullen, S. S.; Takahashi, H.; De Lombaert, S. Bioorg. Med. Chem. Lett. 2011, 21, 4533. doi: 10.1016/j.bmcl.2011.05.126 pmid: 19788239
	(d) Filippakopoulos, P.; Qi, J.; Picaud, S.; Shen, Y.; Smith, W. B.; Fedorov, O.; Morse, E. M.; Keates, T.; Hickman, T. T.; Felletar, I.; Philpott, M.; Munro, S.; Mckeown, M. R.; Wang, Y.; Christie, A. L.; West, N.; Cameron, M. J.; Schwartz, B.; Heightman, T. D.; La Thangue, N.; French, C. A.; Wiest, O.; Kung, A. L.; Knapp, S.; Bradner, J. E. Nature 2010, 468, 1067. doi: 10.1038/nature09504 pmid: 19788239
	(e) Králová, P.; Maloň, M.; Soural, M. ACS Comb. Sci. 2017, 19, 770. doi: 10.1021/acscombsci.7b00134 pmid: 19788239
	(f) Kundu, P.; Mondal, A.; Das, B.; Chowdhury, C. Adv. Synth. Catal. 2015, 357, 3737. doi: 10.1002/adsc.201500661 pmid: 19788239
	(g) Carlier, P. R.; Zhao, H. W.; Macquarrie-Hunter, S. L.; Deguzman, J. C.; Hsu, D. C. J. Am. Chem. Soc. 2006, 128, 15215. pmid: 19788239
	(h) Al-Tel, T. H.; Al-Qawasmeh, R. A.; Schmidt, M. F.; Al-Aboudi, A.; Rao, S. N.; Sabri, S. S.; Voelter, W. J. Med. Chem. 2009, 52, 6484. doi: 10.1021/jm9008482 pmid: 19788239
	(i) Wang, Y. Y.; Ling, B. P.; Liu, P.; Bi, S. W. Organometallics 2018, 37, 3035. doi: 10.1021/acs.organomet.8b00406 pmid: 19788239
[2]	Meanwell, N. A.; Sit, S.-Y.; Gao, J.; Boissard, C. G.; Lum-Ragan, J.; Dworetzky, S. I.; Gribkoff, V. K. Bioorg. Med. Chem. Lett. 1996, 6, 1641.
[3]	(a) P. Barot,, K.; Nikolova, S.; Ivanov, I.; D. Ghate,, M. Mini-Rev. Med. Chem. 2013, 13, 1421. doi: 10.2174/13895575113139990072
	(b) Yu, K.-L.; Sin, N.; Civiello, R. L.; Wang, X. A.; Combrink, K. D.; Gulgeze, H. B.; Venables, B. L.; Wright, J. J. K.; Dalterio, R. A.; Zadjura, L.; Marino, A.; Dando, S.; D’arienzo, C.; Kadow, K. F.; Cianci, C. W.; Li, Z.; Clarke, J.; Genovesi, E. V.; Medina, I.; Lamb, L.; Colonno, R. J.; Yang, Z.; Krystal, M.; Meanwell, N. A. Bioorg. Med. Chem. Lett. 2007, 17, 895. doi: 10.1016/j.bmcl.2006.11.063
	(c) Yu, K.-L.; Wang, X. A.; Civiello, R. L.; Trehan, A. K.; Pearce, B. C.; Yin, Z. W.; Combrink, K. D.; Gulgeze, H. B.; Zhang, Y.; Kadow, K. F.; Cianci, C. W.; Clarke, J.; Genovesi, E. V.; Medina, I.; Lamb, L.; Wyde, P. R.; Krystal, M.; Meanwell, N. A. Bioorg. Med. Chem. Lett. 2006, 16, 1115. doi: 10.1016/j.bmcl.2005.11.109
[4]	(a) Monforte, A.-M.; Logoteta, P.; Ferro, S.; Luca, L. D.; Iraci, N.; Maga, G.; Clercq, E. D.; Pannecouque, C.; Chimirri, A. Biorg. Med. Chem. 2009, 17, 5962. doi: 10.1016/j.bmc.2009.06.068
	(b) Monforte, A.-M.; Logoteta, P.; Luca, L. D.; Iraci, N.; Ferro, S.; Maga, G.; De Clercq, E.; Pannecouque, C.; Chimirri, A. Biorg. Med. Chem. 2010, 18, 1702. doi: 10.1016/j.bmc.2009.12.059
[5]	Gustin, D. J.; Sehon, C. A.; Wei, J. M.; Cai, H.; Meduna, S. P.; Khatuya, H.; Sun, S. Q.; Gu, Y.; Jiang, W.; Thurmond, R. L.; Karlsson, L.; Edwards, J. P. Bioorg. Med. Chem. Lett. 2005, 15, 1687. pmid: 15745822
[6]	Kawamoto, H.; Nakashima, H.; Kato, T.; Arai, S.; Kamata, K.; Iwasawa, Y. Tetrahedron 2001, 57, 981. doi: 10.1016/S0040-4020(00)01064-4
[7]	Diao, X. Q.; Wang, Y. J.; Jiang, Y. W.; Ma, D. W. J. Org. Chem. 2009, 74, 7974. doi: 10.1021/jo9017183
[8]	Mclaughlin, M.; Palucki, M.; Davies, I. W. Org. Lett. 2006, 8, 3311. doi: 10.1021/ol061233j
[9]	Beyer, A.; Reucher, C. M. M.; Bolm, C. Org. Lett. 2011, 13, 2876. doi: 10.1021/ol2008878
[10]	(a) Meng, Y. G.; Wang, B. N.; Ren, L. N.; Zhao, Q. L.; Yu, W. Q.; Chang, J. B. New J. Chem. 2018, 42, 13790. doi: 10.1039/C8NJ03166E
	(b) Yu, J. P.; Gao, C.; Song, Z. X.; Yang, H. J.; Fu, H. Eur. J. Org. Chem. 2015, 2015, 5869. doi: 10.1002/ejoc.201500726
[11]	Youn, S. W.; Kim, Y. H. Org. Lett. 2016, 18, 6140. pmid: 27934371
[12]	Xu, F.; Long, H.; Song, J. S.; Xu, H.-C. Angew. Chem., Int. Ed. 2019, 58, 9017. doi: 10.1002/anie.201904931
[13]	Li, J.-S.; Yang, P.-P.; Xie, X.-Y.; Jiang, S.; Tao, L.; Li, Z.-W.; Lu, C.-H.; Liu, W.-D. Adv. Synth. Catal. 2020, 362, 1977. doi: 10.1002/adsc.202000198
[14]	(a) Lima, H. M.; Lovely, C. J. Org. Lett. 2011, 13, 5736. doi: 10.1021/ol2022438
	(b) Hamm, M. L.; Billig, K. Org. Biomol. Chem. 2006, 4, 4068. doi: 10.1039/B612597B
	(c) Bon, R. S.; Sprenkels, N. E.; Koningstein, M. M.; Schmitz, R. F.; De Kanter, F. J. J.; Dömling, A.; Groen, M. B.; Orru, R. V. A. Org. Biomol. Chem. 2008, 6, 130. doi: 10.1039/B713065A
[15]	Li, D. Z.; Ollevier, T. Org. Lett. 2019, 21, 3572. doi: 10.1021/acs.orglett.9b00973
[16]	Chernyshev, V. M.; Khazipov, O. V.; Shevchenko, M. A.; Chernenko, A. Y.; Astakhov, A. V.; Eremin, D. B.; Pasyukov, D. V.; Kashin, A. S.; Ananikov, V. P. Chem. Sci. 2018, 9, 5564. doi: 10.1039/c8sc01353e pmid: 30061988
[17]	Ruiz, J.; Mesa, A. F. Chem.-Eur. J. 2014, 20, 102. doi: 10.1002/chem.201303773
[18]	Fader, L. D.; Bethell, R.; Bonneau, P.; Bös, M.; Bousquet, Y.; Cordingley, M. G.; Coulombe, R.; Deroy, P.; Faucher, A.-M.; Gagnon, A.; Goudreau, N.; Grand-Maître, C.; Guse, I.; Hucke, O.; Kawai, S. H.; Lacoste, J.-E.; Landry, S.; Lemke, C. T.; Malenfant, E.; Mason, S.; Morin, S.; O’meara, J.; Simoneau, B.; Titolo, S.; Yoakim, C. Bioorg. Med. Chem. Lett. 2011, 21, 398. doi: 10.1016/j.bmcl.2010.10.131 pmid: 21087861
[19]	Eltze, M.; Mutschler, E.; Lambrecht, G. Eur. J. Pharmacol. 1992, 211, 283. pmid: 1377628
[20]	Hargrave, K. D.; Proudfoot, J. R.; Grozinger, K. G.; Cullen, E.; Kapadia, S. R.; Patel, U. R.; Fuchs, V. U.; Mauldin, S. C.; Vitous, J.; Behnke, M. L.; Klunder, J. M.; Pal, K.; Skiles, J. W.; Mcneil, D. W.; Rose, J. M.; Chow, G. C.; Skoog, M. T.; Wu, J. C.; Schmidt, G.; Engel, W. W.; Eberlein, W. G.; Saboe, T. D.; Campbell, S. J.; Rosenthal, A. S.; Adams, J. J. Med. Chem. 1991, 34, 2231. pmid: 1712395
[21]	Pèpe, G.; Reboul, J.-P.; Oddon, Y. Eur. J. Med. Chem. 1989, 24, 1. doi: 10.1016/0223-5234(89)90157-8
[22]	(a) Yuan, S.; Yue, Y.-L.; Zhang, D.-Q.; Zhang, J.-Y.; Yu, B.; Liu, H.-M. Chem. Commun. 2020, 56, 11461. doi: 10.1039/D0CC04875E
	(b) Hwang, J.; Borgelt, L.; Wu, P. ACS Comb. Sci. 2020, 22, 495. doi: 10.1021/acscombsci.0c00173
	(c) Velasco-Rubio, Á.; Varela, J. A.; Saá, C. Adv. Synth. Catal. 2020, 362, 4861. doi: 10.1002/adsc.202000808
	(d) Dagar, A.; Kim, I. Org. Biomol. Chem. 2020, 18, 9836. doi: 10.1039/D0OB02002H
	(e) Archer, G. A.; Sternbach, L. H. Chem. Rev. 1968, 68, 747. doi: 10.1021/cr60256a004
[23]	(a) Chobanian, H. R.; Guo, Y.; Liu, P.; Lanza, T. J.; Chioda, M.; Chang, L.; Kelly, T. M.; Kan, Y. Q.; Palyha, O.; Guan, X.-M.; Marsh, D. J.; Metzger, J. M.; Raustad, K.; Wang, S.-P.; Strack, A. M.; Gorski, J. N.; Miller, R.; Pang, J. M.; Lyons, K.; Dragovic, J.; Ning, J. G.; Schafer, W. A.; Welch, C. J.; Gong, X. Y.; Gao, Y.-D.; Hornak, V.; Reitman, M. L.; Nargund, R. P.; Lin, L. S. Biorg. Med. Chem. 2012, 20, 2845. doi: 10.1016/j.bmc.2012.03.029
	(b) Liu, P.; Lanza, T. J.; Chioda, M.; Jones, C.; Chobanian, H. R.; Guo, Y.; Chang, L.; Kelly, T. M.; Kan, Y. Q.; Palyha, O.; Guan, X.-M.; Marsh, D. J.; Metzger, J. M.; Ramsay, K.; Wang, S.-P.; Strack, A. M.; Miller, R.; Pang, J. M.; Lyons, K.; Dragovic, J.; Ning, J. G.; Schafer, W. A.; Welch, C. J.; Gong, X. Y.; Gao, Y.-D.; Hornak, V.; Ball, R. G.; Tsou, N.; Reitman, M. L.; Wyvratt, M. J.; Nargund, R. P.; Lin, L. S. ACS Med. Chem. Lett. 2011, 2, 933. doi: 10.1021/ml200207w
	(c) Matsufuji, T.; Shimada, K.; Kobayashi, S.; Ichikawa, M.; Kawamura, A.; Fujimoto, T.; Arita, T.; Hara, T.; Konishi, M.; Abe-Ohya, R.; Izumi, M.; Sogawa, Y.; Nagai, Y.; Yoshida, K.; Abe, Y.; Kimura, T.; Takahashi, H. Biorg. Med. Chem. 2015, 23, 89. doi: 10.1016/j.bmc.2014.11.018
	(d) Failli, A. A.; Shumsky, J. S.; Steffan, R. J.; Caggiano, T. J.; Williams, D. K.; Trybulski, E. J.; Ning, X.; Lock, Y.; Tanikella, T.; Hartmann, D.; Chan, P. S.; Park, C. H. Bioorg. Med. Chem. Lett. 2006, 16, 954. doi: 10.1016/j.bmcl.2005.10.107
[24]	Maddess, M. L.; Li, C. M. Organometallics 2019, 38, 81. doi: 10.1021/acs.organomet.8b00322
[25]	Novelli, F.; Sparatore, A.; Tasso, B.; Sparatore, F. Bioorg. Med. Chem. Lett. 1999, 9, 3031. pmid: 10571170
[26]	Shi, F. Q.; Xu, X. X.; Zheng, L. Y.; Dang, Q.; Bai, X. J. Comb. Chem. 2008, 10, 158. doi: 10.1021/cc7002039
[27]	(a) Zhu, H. Q.; Shang, T. B.; Lu, Z. H.; Luo, F.; Zhu, G. G. Chin. J. Org. Chem. 2020, 40, 3410. (in Chinese) doi: 10.6023/cjoc202005066
	( 朱海倩, 商甜波, 卢增辉, 罗芳, 朱钢国, 有机化学, 2020, 40, 3410.) doi: 10.6023/cjoc202005066
	(b) Tian, S. H.; Luo, T.; Zhu, Y. P.; Wan, J.-P. Chin. Chem. Lett. 2020, 31, 3073. doi: 10.1016/j.cclet.2020.07.042
	(c) Fu, L. Q.; Liu, Y. Y.; Wan, J.-P. Org. Lett. 2021, 23, 4363. doi: 10.1021/acs.orglett.1c01301
	(d) Yu, Q.; Liu, Y. Y.; Wan, J.-P. Org. Chem. Front. 2020, 7, 2770. doi: 10.1039/D0QO00855A
	(e) Chen, Q. W.; Yang, Y. C.; Wang, X.; Zhang, Q.; Li, D. Chin. J. Org. Chem. 2020, 40, 451. (in Chinese)
	( 陈倩雯, 杨耀成, 王霞, 张谦, 李栋, 有机化学, 2020, 40, 451.)
	(f) Zhao, B. L.; Liu, Y. Y. Synthesis 2020, 52, 3211. doi: 10.1055/s-0040-1707124
[28]	Tao, S.; Bu, Q. Q.; Shi, Q. Q.; Wei, D. H.; Dai, B.; Liu, N. Chem. Eur. J. 2020, 26, 3252. doi: 10.1002/chem.201905828
[29]	(a) Karthikeyan, J.; Cheng, C.-H. Angew. Chem., Int. Ed. 2011, 50, 9880. doi: 10.1002/anie.201104311
	(b) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. doi: 10.1021/cr900184e
	(c) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094. doi: 10.1002/anie.200806273
	(d) Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int. Ed. 2009, 48, 9792. doi: 10.1002/anie.200902996
	(e) Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215. doi: 10.1021/cr100280d
	(f) Liu, C.; Zhang, H.; Shi, W.; Lei, A. W. Chem. Rev. 2011, 111, 1780. doi: 10.1021/cr100379j
[30]	(a) Liu, Q.; Xie, G. Q.; Wang, Q.; Mo, Z. D.; Li, C.; Ding, S. J.; Wang, X. X. Tetrahedron 2019, 75, 130490. doi: 10.1016/j.tet.2019.130490
	(b) Minisci, F.; Citterio, A.; Giordano, C. Acc. Chem. Res. 1983, 16, 27. doi: 10.1021/ar00085a005
	(c) Yan, K.; Yang, D. S.; Wei, W.; Wang, F.; Shuai, Y. Y.; Li, Q. N.; Wang, H. J. Org. Chem. 2015, 80, 1550. doi: 10.1021/jo502474z
	(d) Mandal, S.; Bera, T.; Dubey, G.; Saha, J.; Laha, J. K. ACS Catal. 2018, 8, 5085. doi: 10.1021/acscatal.8b00743
	(e) Zhang, Z.; Jia, C.; Kong, X.; Hussain, M.; Liu, Z.; Liang, W.; Jiang, L.; Jiang, H.; Ma, J. ACS Sustainable Chem. Eng. 2020, 8, 16463. doi: 10.1021/acssuschemeng.0c05118
	(f) Zhu, Y. C.; Huang, K. M.; Pan, J.; Qiu, X.; Luo, X.; Qin, Q. X.; Wei, J. L.; Wen, X. J.; Zhang, L. Z.; Jiao, N. Nat. Commun. 2018, 9, 2625. doi: 10.1038/s41467-018-05014-w
[31]	(a) Shi, Z. Z.; Glorius, F. Chem. Sci. 2013, 4, 829. doi: 10.1039/C2SC21823B
	(b) Wang, X. Y.; Wang, S. C.; Gao, Y. M.; Sun, H.; Liang, X. A.; Bu, F. X.; Abdelilah, T.; Lei, A. W. Org. Lett. 2020, 22, 5429. doi: 10.1021/acs.orglett.0c01796
	(c) Chen, Z. C.; Zhang, H.; Zhou, S. F.; Cui, X. L. Chin. J. Org. Chem. 2020, 40, 3866. (in Chinese) doi: 10.6023/cjoc202007005
	( 陈志超, 张红, 周树锋, 崔秀灵, 有机化学, 2020, 40, 3866.) doi: 10.6023/cjoc202007005
[32]	(a) Yi, H.; Zhang, G. T.; Wang, H. M.; Huang, Z. Y.; Wang, J.; Singh, A. K.; Lei, A. W. Chem. Rev. 2017, 117, 9016. doi: 10.1021/acs.chemrev.6b00620
	(b) Pan, G.-A.; Li, Y.; Li, J.-H. Org. Chem. Front. 2020, 7, 2486. doi: 10.1039/D0QO00651C
[33]	(a) Hollóczki, O.; Terleczky, P.; Szieberth, D.; Mourgas, G.; Gudat, D.; Nyulászi, L. J. Am. Chem. Soc. 2011, 133, 780. doi: 10.1021/ja103578y pmid: 21174475
	(b) Tao, S.; Guo, C.; Liu, N.; Dai, B. Organometallics 2017, 36, 4432. doi: 10.1021/acs.organomet.7b00651 pmid: 21174475
[34]	(a) Khan, D.; Mukhtar, S.; Alsharif, M. A.; Alahmdi, M. I.; Ahmed, N. Tetrahedron Lett. 2017, 58, 3183. doi: 10.1016/j.tetlet.2017.07.018
	(b) Prasad, V.; Kale, R. R.; Mishra, B. B.; Kumar, D.; Tiwari, V. K. Org. Lett. 2012, 14, 2936. doi: 10.1021/ol3012315
[35]	Chen, F.; Chen, D. T.; Shi, L.; Liu, N.; Dai, B. J. CO₂ Util. 2016, 16, 391.
[36]	Wang, Y.-B.; Liu, B.-Y.; Bu, Q. Q.; Dai, B.; Liu, N. Adv. Synth. Catal. 2020, 362, 2930. doi: 10.1002/adsc.202000186

Entry	2a, Condition A^a	2a, Condition B^b	3a, Condition C^c
1	2a, 80%; (3a, 0)	2a, 82%	3a, 68%; (2a, trace)
2	No K₂S₂O₈, 2a, 0 No base, 2a, 8%	No PhI(OAc)₂, 2a, 0	No K₂S₂O₈, 3a, 0 No base, 3a, trace
3	LiOt-Bu instead of NaOAc, 2a, 12% Na₂CO₃ instead of NaOAc, 2a, 10% KHCO₃ instead of NaOAc, 2a, trace K₂CO₃ instead of NaOAc, 2a, 11%	—	LiOt-Bu instead of NaHCO₃, 3a, 26% Na₂CO₃ instead of NaHCO₃, 3a, 29% KHCO₃ instead of NaHCO₃, 3a, 10% K₂CO₃ instead of NaHCO₃, 3a, 22%
4	DCE instead of MeCN, 2a, 30% DMSO instead of MeCN, 2a, 26% 1,4-Dioxane instead of MeCN, 2a, 35% MeCN/H₂O (V∶V=1∶1), 2a, 36%	DCE instead of MeCN, 2a, 69% DMSO instead of MeCN, 2a, 80% 1,4-Dioxane instead of MeCN, 2a, 77% MeCN/H₂O (V∶V=1∶1), 2a, 40%	DCE instead of MeCN, 3a, 40% DMSO instead of MeCN, 3a, 15% 1,4-Dioxane instead of MeCN, 3a, 10% MeCN/H₂O (V∶V=1∶1), 3a, 26%
5	Na₂S₂O₈ instead of K₂S₂O₈, 2a, 39% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 2a, 45% DDQ instead of K₂S₂O₈, 2a, 0 TBHP instead of K₂S₂O₈, 2a, 0	Na₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 (NH₄)₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 DDQ instead of PhI(OAc)₂, 2a, 0 TBHP instead of PhI(OAc)₂, 2a, 0	Na₂S₂O₈ instead of K₂S₂O₈, 3a, 38% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 3a, 32% DDQ instead of K₂S₂O₈, 3a, 0 TBHP instead of K₂S₂O₈, 3a, trace
6	K₂S₂O₈ (1.0 equiv.), 2a, 65% K₂S₂O₈ (1.5 equiv.), 2a, 80% K₂S₂O₈ (2.0 equiv.), 2a, 79%	PhI(OAc)₂ (1.0 equiv.), 2a, 47% PhI(OAc)₂ (1.5 equiv.), 2a, 82% PhI(OAc)₂ (2.0 equiv.), 2a, 84%	K₂S₂O₈ (1.0 equiv.), 3a, 36% K₂S₂O₈ (1.5 equiv.), 3a, 61% K₂S₂O₈ (2.0 equiv.), 3a, 23%
7	NaOAc (1.5 equiv.), 2a, 69% NaOAc (2.0 equiv.), 2a, 80% NaOAc (3.0 equiv.), 2a, 78%	—	NaHCO₃ (1.5 equiv.), 3a, 61% NaHCO₃ (2.0 equiv.), 3a, 69% NaHCO₃ (3.0 equiv.), 3a, 67%
8	100 ℃ instead of 80 ℃, 2a, 80% 50 ℃ instead of 80 ℃, 2a, 58%	50 ℃ instead of r.t., 2a, 85%	100 ℃ instead of 80 ℃, 3a, 65% 50 ℃ instead of 80 ℃, 3a, 47%
9	—	—	Air, 3a, 59%
10	48 h, 2a, 80%	5 h, 2a, 80%	48 h, 3a, 65%

Entry	2a, Condition A^a	2a, Condition B^b	3a, Condition C^c
1	2a, 80%; (3a, 0)	2a, 82%	3a, 68%; (2a, trace)
2	No K₂S₂O₈, 2a, 0 No base, 2a, 8%	No PhI(OAc)₂, 2a, 0	No K₂S₂O₈, 3a, 0 No base, 3a, trace
3	LiOt-Bu instead of NaOAc, 2a, 12% Na₂CO₃ instead of NaOAc, 2a, 10% KHCO₃ instead of NaOAc, 2a, trace K₂CO₃ instead of NaOAc, 2a, 11%	—	LiOt-Bu instead of NaHCO₃, 3a, 26% Na₂CO₃ instead of NaHCO₃, 3a, 29% KHCO₃ instead of NaHCO₃, 3a, 10% K₂CO₃ instead of NaHCO₃, 3a, 22%
4	DCE instead of MeCN, 2a, 30% DMSO instead of MeCN, 2a, 26% 1,4-Dioxane instead of MeCN, 2a, 35% MeCN/H₂O (V∶V=1∶1), 2a, 36%	DCE instead of MeCN, 2a, 69% DMSO instead of MeCN, 2a, 80% 1,4-Dioxane instead of MeCN, 2a, 77% MeCN/H₂O (V∶V=1∶1), 2a, 40%	DCE instead of MeCN, 3a, 40% DMSO instead of MeCN, 3a, 15% 1,4-Dioxane instead of MeCN, 3a, 10% MeCN/H₂O (V∶V=1∶1), 3a, 26%
5	Na₂S₂O₈ instead of K₂S₂O₈, 2a, 39% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 2a, 45% DDQ instead of K₂S₂O₈, 2a, 0 TBHP instead of K₂S₂O₈, 2a, 0	Na₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 (NH₄)₂S₂O₈ instead of PhI(OAc)₂, 2a, 0 DDQ instead of PhI(OAc)₂, 2a, 0 TBHP instead of PhI(OAc)₂, 2a, 0	Na₂S₂O₈ instead of K₂S₂O₈, 3a, 38% (NH₄)₂S₂O₈ instead of K₂S₂O₈, 3a, 32% DDQ instead of K₂S₂O₈, 3a, 0 TBHP instead of K₂S₂O₈, 3a, trace
6	K₂S₂O₈ (1.0 equiv.), 2a, 65% K₂S₂O₈ (1.5 equiv.), 2a, 80% K₂S₂O₈ (2.0 equiv.), 2a, 79%	PhI(OAc)₂ (1.0 equiv.), 2a, 47% PhI(OAc)₂ (1.5 equiv.), 2a, 82% PhI(OAc)₂ (2.0 equiv.), 2a, 84%	K₂S₂O₈ (1.0 equiv.), 3a, 36% K₂S₂O₈ (1.5 equiv.), 3a, 61% K₂S₂O₈ (2.0 equiv.), 3a, 23%
7	NaOAc (1.5 equiv.), 2a, 69% NaOAc (2.0 equiv.), 2a, 80% NaOAc (3.0 equiv.), 2a, 78%	—	NaHCO₃ (1.5 equiv.), 3a, 61% NaHCO₃ (2.0 equiv.), 3a, 69% NaHCO₃ (3.0 equiv.), 3a, 67%
8	100 ℃ instead of 80 ℃, 2a, 80% 50 ℃ instead of 80 ℃, 2a, 58%	50 ℃ instead of r.t., 2a, 85%	100 ℃ instead of 80 ℃, 3a, 65% 50 ℃ instead of 80 ℃, 3a, 47%
9	—	—	Air, 3a, 59%
10	48 h, 2a, 80%	5 h, 2a, 80%	48 h, 3a, 65%

碱性调控的选择性: 通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物

Basicity-Tuned Selectivity: Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

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