Pd/Mengphos-Catalyzed High-Order [4+4] Cycloaddition for Efficient Synthesis of Oxazocines

Yinggao Meng; Mengya Xu; Yingying Xia; Huiwen Mei; Xiucheng Bi; Xin Zhou; Xin Han

doi:10.1055/a-2435-5589

Synthesis, Table of Contents

Synthesis 2024; 56(24): 3870-3878
DOI: 10.1055/a-2435-5589

paper

Pd/Mengphos-Catalyzed High-Order [4+4] Cycloaddition for Efficient Synthesis of Oxazocines

Yinggao Meng∗

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

,

Mengya Xu

^bCollege of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Yingying Xia

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

,

Huiwen Mei

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

,

Xiucheng Bi

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

,

Xin Zhou

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

,

Xin Han∗

^aShiyan Key Laboratory of Biological Resources and Eco-environmental Protection, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, P. R. of China

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Abstract

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Abstract

The development of new catalytic systems that enable regio- and chemoselective construction of diversely functionalized oxazocines is an important topic in organic synthesis and pharmacochemistry. Herein, a novel Pd/Mengphos complex was designed and applied in a palladium-catalyzed high-order [4+4] cycloaddition of 2-substituted allylic carbonates to α,β-unsaturated imines, allowing facile access to versatile oxazocines in good yields with excellent b/l and Z/E selectivities (up to 92% yield and complete b/l and Z/E selectivities). The reaction exhibited a broad substrate scope, mild reaction conditions, and good functional group compatibility. In addition, an asymmetric version has also been tested, affording the desired oxazocines in moderate to good enantioselectivity.

Key words

palladium catalysis - Mengphos - [4+4] cycloaddition - α,β-unsaturated imines - allyl carbonates - oxazocines

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References

References
1 Liu Y, Li W, Zhang J. Nat. Sci. Rev. 2017; 4: 326
2 Comprehensive Asymmetric Catalysis, Suppls. I–II., Vols. I–III. Jacobsen EN, Pfaltz A, Yamamoto H. Springer; New York: 1999

For selected reviews, see:

3a Guo M, Zhang P, Li E.-Q. Top. Curr. Chem. 2023; 381: 33
3b Wang Q, Meng Y, Wu L, Li E.-Q. Chin. Chem. Lett. 2023; 34: 108544
3c Hashimoto T, Maruoka K. Chem. Rev. 2015; 115: 5366
3d You Y, Li Q, Zhang YP, Zhao JQ, Wang ZH, Yuan WC. ChemCatChem 2022; 14: e202101887
3e Bagherinejad A, Alizadeh A. Org. Biomol. Chem. 2022; 20: 7188
3f Trost BM, Mata G. Acc. Chem. Res. 2020; 53: 1293
3g Han X, Lin P, Li Q. Chin. Chem. Lett. 2019; 30: 1495
3h Duan J, Li Y.-F, Ding C.-H. Chin. Chem. Lett. 2023; 34: 108401

For selected examples, see:

4a Trost BM, Jiao Z, Liu Y, Min C, Hung C.-IJ. J. Am. Chem. Soc. 2020; 142: 18628
4b Trost BM, Bai W.-J, Hohn C, Bai Y, Cregg JJ. J. Am. Chem. Soc. 2018; 140: 6710
4c Trost BM, Wang Y, Hung C.-IJ. Nat. Chem. 2020; 12: 294
4d Chen Z.-C, Chen Z, Yang Z.-H, Guo L, Du W, Chen Y.-C. Angew. Chem. Int. Ed. 2019; 58: 15021
4e Zhu J.-X, Chen Z.-C, Du W, Chen Y.-C. Angew. Chem. Int. Ed. 2022; 61: e202200880
4f Xiao B.-X, Jiang B, Yan R.-J, Zhu J.-X, Xie K, Gao X.-Y, Ouyang Q, Du W, Chen Y.-C. J. Am. Chem. Soc. 2021; 143: 4809
4g Shen L, Zheng Y, Lin Z, Qin T, Huang Z, Zi W. Angew. Chem. Int. Ed. 2023; 62: e202217051
4h Zheng Y, Qin T, Zi W. J. Am. Chem. Soc. 2021; 143: 1038
4i Li M.-M, Qu BE, Xiao Y.-Q, Xiao W.-J, Lu L.-Q. Sci. Bull. 2021; 66: 1719
4j Shi B, Liu J.-B, Wang Z.-T, Wang L, Lan Y, Lu L.-Q, Xiao W.-J. Angew. Chem. Int. Ed. 2022; 61: e202117215

5a Kumari P, Liu W, Wang C.-J, Dai J, Wang M.-X, Yang Q.-Q, Deng Y.-H, Shao Z. Chin. J. Chem. 2020; 38: 151
5b Liu Y, Wang Z, Huang Z, Zheng X, Yang W, Deng W. Angew. Chem. Int. Ed. 2020; 59: 1238
5c Trost BM, Huang Z, Murhade GM. Science 2018; 362: 564

6a Liu H, Liu Y, Yuan C, Wang G.-P, Zhu S.-F, Wu Y, Wang B, Sun Z, Xiao Y, Zhou Q.-L, Guo H. Org. Lett. 2016; 18: 1302
6b Zhao H.-W, Tian T, Pang H.-L, Li B, Chen X.-Q, Yang Z, Meng W, Song X.-Q, Zhao Y.-D, Liu Y.-Y. Adv. Synth. Catal. 2016; 358: 2619
6c Liu Y, Yang W, Wu Y, Mao B, Gao X, Liu H, Sun Z, Xiao Y, Guo H. Adv. Synth. Catal. 2016; 358: 2867
6d Chen Y, Zang M, Wang W, Liu Y.-Z, Luo X, Deng W.-P. Chin. J. Chem. 2023; 41: 2825
6e Yang W.-L, Huang Z, Liu Y.-Z, Yu X, Deng W.-P. Chin. J. Chem. 2020; 38: 1571

7 Mao B, Liu H, Yan Z, Xu Y, Xu J, Wang W, Wu Y, Guo H. Angew. Chem. Int. Ed. 2020; 59: 11316
8 Shintani R, Moriya K, Hayashi T. Chem. Commun. 2011; 47: 3057
9 Xu J, Shi W, Liu M, Liao J, Wang W, Wu Y, Guo H. Adv. Synth. Catal. 2022; 364: 2060

10a Uno H, Kawai K, Araki T, Shiro M, Shibata N. Angew. Chem. Int. Ed. 2022; 61: e202117635
10b Xie H, Chen L, Han Z, Yang Z, Sun J, Huang H. Org. Lett. 2023; 25: 5011

11a Faller JW, Tully MT. J. Am. Chem. Soc. 1972; 94: 2676
11b Faller JW, Thomsen ME, Mattina MJ. J. Am. Chem. Soc. 1971; 93: 2642

12 Yang Y, Zhu B, Zhu L, Jiang Y, Guo C, Gu J, Ouyang Q, Du W, Chen Y. Chem. Sci. 2021; 12: 11399

13a Jia S, Ma M, Li E.-Q, Duan Z, Mathey F. Org. Lett. 2021; 23: 3337
13b Gan Z, Zhi M, Han R, Li E.-Q, Duan Z, Mathey F. Org. Lett. 2019; 21: 2782
13c Zhi M, Gan Z, Ma R, Cui H, Li E.-Q, Duan Z, Mathey F. Org. Lett. 2019; 21: 3210
13d Cui H, Li K, Wang Y, Song M, Wang C, Wei D, Li E.-Q, Duan Z, Mathey F. Org. Biomol. Chem. 2020; 18: 3740
13e Wang Y, Li E, Duan Z. Chem. Sci. 2022; 13: 8131
13f Meng Q, Meng Y, Liu Q, Yu B, Li Z.-J, Li E.-Q, Zhang J. Adv. Sci. 2024; 2402170

14 Meng Y, Wang Q, Yao X, Wei D, Liu Y.-G, Li E.-Q, Duan Z. Org. Lett. 2022; 24: 9205
15 CCDC 2158695 (3aa) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures

Supplementary Material

Supporting Information