Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes: Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones

doi:10.6023/cjoc202208021

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (10): 3382-3389.DOI: 10.6023/cjoc202208021 Previous Articles Next Articles

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钯催化烯烃的不对称Aza-Wacker反应: 高效合成手性1,3-噁嗪烷-2-酮

杨新拓^a, 陈品红^a, 刘国生^*()

a 中国科学院上海有机化学研究所金属有机化学国家重点实验室沪港化学合成联合实验室分子合成科学卓越创新中心中国科学院大学上海 200032
b 华东师范大学庄长恭研究所上海 200062

收稿日期:2022-08-16 修回日期:2022-10-09 发布日期:2022-11-02
通讯作者: 刘国生
基金资助:
国家重点研发计划(2021YFA1500050); 国家自然科学基金(21971255); 国家自然科学基金(91956202); 国家自然科学基金(21790330); 国家自然科学基金(21821002); 中国科学院前沿科学重点研究计划(QYZDJSSW-SLH055); 中国科学院国际伙伴计划(121731KYSB20190016)

Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes: Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones

Xintuo Yang^a, Pinhong Chen^a, Guosheng Liu()

a State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
b Chang-Kung Chuang Institute, East China Normal University, Shanghai 200062

Received:2022-08-16 Revised:2022-10-09 Published:2022-11-02
Contact: Guosheng Liu
Supported by:
National Key R&D Program of China(2021YFA1500050); National Natural Science Foundation of China(21971255); National Natural Science Foundation of China(91956202); National Natural Science Foundation of China(21790330); National Natural Science Foundation of China(21821002); Science and Technology Commission of Shanghai Municipality(19590750400); Science and Technology Commission of Shanghai Municipality(21520780100); Science and Technology Commission of Shanghai Municipality(17JC1401200); Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDJSSW-SLH055); International Partnership Program of Chinese Academy of Sciences(121731KYSB20190016)

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Abstract

A Pd-catalyzed asymmetric aza-Wacker-type reaction with N-Ts carbamate as the nucleophile has been developed, which employed a C-6 substituted pyridinyl-oxazoline as the chiral ligand and benzoquinone (BQ) as the oxidant. This reaction provides an efficient access to chiral 1,3-oxazinan-2-ones with good efficiency and excellent enantioselectivity. Mechanistic studies indicated that the reaction is initiated by an intramolecular asymmetric aminopalladation.

Key words: aza-Wacker, palladium catalysis, asymmetric aminopalladation, chiral 1,3-oxazinan-2-ones, chiral pyridinyl- oxazoline

Cite this article

Xintuo Yang, Pinhong Chen, Guosheng Liu. Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes: Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3382-3389.

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Fig. & Tab. 5

Figure 1. Drugs bearing chiral 1,3-oxazinan-2-ones and 1,3- amino alcohols

Scheme 1. Asymmetric Pd-catalyzed intramolecular aza-Wacker reactions of alkenes

Entry	Ligand	Solvent	Yield^b/%	ee^c/%
1	L1	DCE	86	51
2	L2	DCE	81	57
3	L3	DCE	66	50
4	L4	DCE	70	78
5	L5	DCE	68	84
6	L6	DCE	53	77
7	L5	DCM	66	81
8	L5	TCE	69	83
9	L5	Toluene	85	80
10	L5	Benzene	90	80
11	L5	PhCl	87	84
12	L5	PhCF₃	96	85
13	L5	THF	44	91
14	L5	Dioxane	43	94
15	L5	PhCF₃/dioxane (V∶V=1∶4)	85	94

Table 1. Optimization of the reaction conditions of asymmetric palladium-catalyzed Aza-Wacker reaction

Table 2. Substrates scope of asymmetric palladium-catalyzed Aza-Wacker reaction

Scheme 2. Mechanistic studies of asymmetric palladium-catalyzed Aza-Wacker reaction

References 18

[1]	(a) Duer, W. C.; Bertrand, G. L. J. Am. Chem. Soc. 1970, 92, 2588. doi: 10.1021/ja00711a085 pmid: 16821799
	(b) Meyer, A.; Brunjes, M.; Taft, F.; Frenzel, T.; Sasse, F.; Kirschning, A. Org. Lett. 2007, 9, 1489. pmid: 16821799
	(c) Widdison, W. C.; Wilhelm, S. D.; Cavanagh, E. E.; Whiteman, K. R.; Leece, B. A.; Kovtun, Y.; Goldmacher, V. S.; Xie, H.; Steeves, R. M.; Lutz, R.; Zhao, R.; Wang, L.; Blättler, W. A.; Chari, R. V. J. J. Med. Chem. 2006, 49, 4392. pmid: 16821799
[2]	(a) Sham, H. L.; Betebenner, D. A.; Rosenbrook, W.; Herrin, T.; Saldivar, A.; Vasavanonda, S.; Plattner, J. J.; Norbeck, D. W. Bioorg. Med. Chem. Lett. 2004, 14, 2643. doi: 10.1016/j.bmcl.2004.02.089
	(b) Kondo, S.; Shibahara, S.; Takahashi, S.; Maeda, K.; Umezawa, H.; Ohno, M. J. Am. Chem. Soc. 1970, 92, 2588. doi: 10.1021/ja00711a085
[3]	(a) Harayama, H.; Abe, A.; Sakado, T.; Kimura, M.; Fugami, K.; Tanaka, S.; Tamaru, T. J. Org. Chem. 1997, 62, 2113. pmid: 15913354
	(b) Lei, A.; Lu, X.; Liu, G. Tetrahedron Lett. 2004, 45, 1785. doi: 10.1016/j.tetlet.2003.12.109 pmid: 15913354
	(c) Alexanian, E. J.; Lee, C.; Sorensen, E. J. J. Am. Chem. Soc. 2005, 127, 7690. pmid: 15913354
	(d) Zhu, H.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2014, 136, 1766. doi: 10.1021/ja412023b pmid: 15913354
	(e) Nicolai, S.; Piemontesi, S.; Waser, J. Angew. Chem., Int. Ed. 2011, 50, 4680. doi: 10.1002/anie.201100718 pmid: 15913354
	(f) Ma, R.; Young, J.; Promontorio, R.; Dannheim, F. M.; Pattillo, C. C.; White, M. C. J. Am. Chem. Soc. 2019, 141, 9468. doi: 10.1021/jacs.9b02690 pmid: 15913354
[4]	Bunno, Y.; Tsukimawashi, Y.; Kojima, M.; Yoshino, T.; Matsunaga, S. ACS Catal. 2021, 11, 2663. doi: 10.1021/acscatal.0c05261
[5]	(a) Kotov, V.; Scarborough, C. C.; Stahl, S. S. Inorg. Chem. 2007, 46, 1910. doi: 10.1021/ic061997v pmid: 21428440
	(b) McDonald, R. I.; Liu, G.; Stahl, S. S. Chem. Rev. 2011. 111, 2981. doi: 10.1021/cr100371y pmid: 21428440
[6]	Thomas, A. A.; Nagamalla, S.; Sathyamoorthi, S. Chem. Sci. 2020, 11, 8073. doi: 10.1039/d0sc02554b pmid: 34123081
[7]	Jiang, F.; Wu, Z.; Zhang, W. Tetrahedron Lett. 2010, 51, 5124. doi: 10.1016/j.tetlet.2010.07.084
[8]	(a) McDonald, R. I.; White, P. B.; Weinstein, A. B.; Tam. C. P.; Stahl, S. S. Org. Lett. 2011, 13, 2830. doi: 10.1021/ol200784y pmid: 21534607
	(b) Weinstein, A. B.; Stahl, S. S. Angew. Chem., Int. Ed. 2012, 51, 11505. doi: 10.1002/anie.201206702 pmid: 21534607
[9]	(a) Ramalingan, C.; Takenaka, K.; Sasai, H. Tetrahedron 2011, 67, 2889. doi: 10.1016/j.tet.2011.02.057
	(b) Sen, A.; Takenaka, K.; Sasai, H. Org. Lett. 2018, 20, 6827. doi: 10.1021/acs.orglett.8b02946
[10]	Yang, G.; Shen, C.; Zhang, W. Angew. Chem., Int. Ed. 2012, 51, 9141. doi: 10.1002/anie.201203693
[11]	Kou, X.; Shao, Q.; Ye, C.; Yang, G.; Zhang, W. J. Am. Chem. Soc. 2018, 140, 7587. doi: 10.1021/jacs.8b02865
[12]	(a) Yip, K.-T.; Yang, M.; Law, K.-L.; Zhu, N.-Y.; Yang, D. J. Am. Chem. Soc. 2006, 128, 3130. doi: 10.1021/ja060291x
	(b) He, W.; Yip, K.-T.; Zhu, N.-Y.; Yang, D. Org. Lett. 2009, 11, 5626. doi: 10.1021/ol902348t
	(c) Du, W.; Gu, Q.; Li, Y.; Lin, Z.; Yang, D. Org. Lett. 2017, 19, 316. doi: 10.1021/acs.orglett.6b03410
[13]	Joosten, A.; Persson, A.; Millet, R.; Johnson, M.; Bäckvall, J.-E. Chem.-Eur. J. 2012, 18, 15151. doi: 10.1002/chem.201202359
[14]	(a) Qi, Xiao.; Chen, C.; Hou, C.; Fu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2018, 140, 7415. doi: 10.1021/jacs.8b03767
	(b) Chen, C.; Pfluger, P.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2019, 58, 2392. doi: 10.1002/anie.201813591
	(c) Hou, C.; Chen, C.; Liu, G. Angew. Chem., Int. Ed. 2020, 59, 2735. doi: 10.1002/anie.201913100
	(d) Li, X.; Qi, X.; Hou, C.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2020, 59, 17239. doi: 10.1002/anie.202006757
	(e) Chen, C.; Hou, C., Chen, P.; Liu, G. Chin. J. Chem. 2020, 38, 346. doi: 10.1002/cjoc.201900516
[15]	Tian, B.; Chen, P.; Liu, G. Synlett 2022, 33, 927. doi: 10.1055/s-0040-1719898
[16]	(a) Tian, B.; Chen, P.; Leng, X.; Liu, G. Nat. Catal. 2021, 4, 172. doi: 10.1038/s41929-021-00574-5
	(b) Tian, B.; Li, Xiang.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2021, 60, 14881. doi: 10.1002/anie.202104252
[17]	Yang, X.; Li, X.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2022, 144, 7972. doi: 10.1021/jacs.2c02753
[18]	Jiang, C.; Covell, D. J.; Stepan, A. F.; Plummer, M. S.; White, C. M. Org. Lett. 2012, 14, 1386. doi: 10.1021/ol300063t pmid: 22360547

钯催化烯烃的不对称Aza-Wacker反应: 高效合成手性1,3-噁嗪烷-2-酮

Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes: Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones

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