Abstract
A highly efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed, which exhibits good functional group compatibility, high atomic and step economy. This protocol utilizes a strategy of synergistic catalysis with a chiral N,N′-dioxide/NiII complex and an achiral Pd0 catalyst, generating a series of multi-substituted allylic alcohols with a quaternary carbon stereocenter in high yield and excellent regio-, Z/E- and enantioselectivity under mild conditions. Further transformations of the product demonstrate the potential utility of this protocol in the synthesis of allyl alcohol derivatives and natural product analogues. Experimental studies revealed that the N,N′-dioxide/metal complexes play an important role in controlling the Z/E- and enantioselectivity. The density functional theory (DFT) calculations further demonstrated that multiple C-H···π interactions between the aromatic rings of the two substrates and the amide moiety in the ligand stabilized the dominant transition state.
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Trost BM, Crawley ML. Chem Rev, 2003, 103: 2921–2944
Trost BM, Machacek MR, Aponick A. Acc Chem Res, 2006, 39: 747–760
Trost BM, Fandrick DR. Chemlnform, 2008, 39: 59–72
Lu Z, Ma S. Angew Chem Int Ed, 2008, 47: 258–297
Liu Y, Han SJ, Liu WB, Stoltz BM. Acc Chem Res, 2015, 48: 740–751
Süsse L, Stoltz BM. Chem Rev, 2021, 121: 4084–4099
Pàmies O, Margalef J, Cañellas S, James J, Judge E, Guiry PJ, Moberg C, Bäckvall JE, Pfaltz A, Pericàs MA, Diéguez M. Chem Rev, 2021, 121: 4373–4505
Wei L, Wang CJ. Chem Catal, 2023, 3: 100455
Wang PS, Gong LZ. Chin J Chem, 2023, 41: 1841–1848
Trost BM, Thaisrivongs DA, Donckele EJ. Angew Chem Int Ed, 2013, 52: 1523–1526
Lin HC, Wang PS, Tao ZL, Chen YG, Han ZY, Gong LZ. J Am Chem Soc, 2016, 138: 14354–14361
Hu RB, Wang CH, Ren W, Liu Z, Yang SD. ACS Catal, 2017, 7: 7400–7404
Rieckhoff S, Meisner J, Kästner J, Frey W, Peters R. Angew Chem Int Ed, 2018, 57: 1404–1408
Matsui JK, Gutiérrez-Bonet Á, Rotella M, Alam R, Gutierrez O, Molander GA. Angew Chem Int Ed, 2018, 57: 15847–15851
Fan LF, Luo SW, Chen SS, Wang TC, Wang PS, Gong LZ. Angew Chem Int Ed, 2019, 58: 16806–16810
Lin HC, Xie PP, Dai ZY, Zhang SQ, Wang PS, Chen YG, Wang TC, Hong X, Gong LZ. J Am Chem Soc, 2019, 141: 5824–5834
Zhang J, Yang WL, Zheng H, Wang Y, Deng WP. Angew Chem Int Ed, 2022, 61: e202117079
Jiang R, Zhao QR, Zheng C, You SL. Nat Catal, 2022, 5: 1089–1097
Xiao L, Chang X, Xu H, Xiong Q, Dang Y, Wang CJ. Angew Chem Int Ed, 2022, 61: e202212948
Tian K, Chang X, Xiao L, Dong XQ, Wang CJ. Fundamental Res, 2022, doi: https://doi.org/10.1016/j.fmre.2022.07.008
Higashida K, Smaïl V, Nagae H, Carpentier JF, Mashima K. ACS Catal, 2023, 13: 2156–2161
Qi J, Song T, Yang Z, Sun S, Tung CH, Xu Z. ACS Catal, 2023, 13: 2555–2564
Nilova A, Mannchen MD, Noel AN, Semenova E, Grenning AJ. Chem Sci, 2023, 14: 2755–2762
Ke M, Yu Y, Sun L, Li X, Cao Q, Xiao X, Chen F. Chem Commun, 2023, 59: 2632–2635
Marshall JA. Chem Rev, 1989, 89: 1503–1511
He J, Ling J, Chiu P. Chem Rev, 2014, 114: 8037–8128
Du Q, Zhang L, Gao F, Wang L, Zhang W. Chin J Org Chem, 2022, 42: 3240–3262
Xu J, Song Y, He J, Dong S, Lin L, Feng X. Angew Chem Int Ed, 2021, 60: 14521–14527
Xu J, Song Y, Yang J, Yang B, Su Z, Lin L, Feng X. Angew Chem Int Ed, 2023, 62: e202217887
Niu B, Wei Y, Shi M. Org Chem Front, 2021, 8: 3475–3501
Yang C, Yang ZX, Ding CH, Xu B, Hou XL. Chem Record, 2021, 21: 1442–1454
Shaghafi MB, Grote RE, Jarvo ER. OrgLett, 2011, 13: 5188–5191
Liu Z, Feng X, Du H. Org Lett, 2012, 14: 3154–3157
Ma C, Huang Y, Zhao Y. ACS Catal, 2016, 6: 6408–6412
Cheng Q, Zhang HJ, Yue WJ, You SL. Chem, 2017, 3: 428–436
Suo JJ, Du J, Liu QR, Chen D, Ding CH, Peng Q, Hou XL. Org Lett, 2017, 19: 6658–6661
Cheng Q, Zhang F, Cai Y, Guo YL, You SL. Angew Chem Int Ed, 2018, 57: 2134–2138
Wang YN, Yang LC, Rong ZQ, Liu TL, Liu R, Zhao Y. Angew Chem Int Ed, 2018, 57: 1596–1600
Peng Y, Huo X, Luo Y, Wu L, Zhang W. Angew Chem Int Ed, 2021, 60: 24941–24949
Sarkar T, Talukdar K, Das BK, Shah TA, Debnath B, Punniyamurthy T. Org Biomol Chem, 2021, 19: 3776–3790
Trost BM, Bunt RC, Lemoine RC, Calkins TL. J Am Chem Soc, 2000, 122: 5968–5976
Trost BM, Tang W, Schulte JL. Org Lett, 2000, 2: 4013–4015
Miyashita M, Mizutani T, Tadano G, Iwata Y, Miyazawa M, Tanino K. Angew Chem Int Ed, 2005, 44: 5094–5097
Alibés R, Bayón P, de March P, Figueredo M, Font J, García-García E, González-Gálvez D. Org Lett, 2005, 7: 5107–5109
Raghunath M, Zhang X. Tetrahedron Lett, 2005, 46: 8213–8216
Trost BM, Zhang T. Org Lett, 2006, 8: 6007–6010
Hale KJ, Manaviazar S, George JH, Walters MA, Dalby SM. Org Lett, 2009, 11: 733–736
Mangion I, Strotman N, Drahl M, Imbriglio J, Guidry E. Org Lett, 2009, 11: 3258–3260
Li G, Feng X, Du H. Org Biomol Chem, 2015, 13: 5826–5830
Hu W, Lin Z, Wang C. Org Lett, 2022, 24: 5751–5755
Trost BM, Jiang C. J Am Chem Soc, 2001, 123: 12907–12908
Du C, Li L, Li Y, Xie Z. Angew Chem Int Ed, 2009, 48: 7853–7856
Doyle MGJ, Gabbey AL, McNutt W, Lundgren RJ. Angew Chem Int Ed, 2021, 60: 26495–26499
Song C, Zhang HH, Yu S. ACS Catal, 2022, 12: 1428–1432
Wang Y, Chai J, You C, Zhang J, Mi X, Zhang L, Luo S. J Am Chem Soc, 2020, 142: 3184–3195
Trost BM, Molander GA. J Am Chem Soc, 1981, 103: 5969–5972
Tsuji J, Kataoka H, Kobayashi Y. Tetrahedron Lett, 1981, 22: 2575–2578
Zhang X, You R, Wei Z, Jiang X, Yang J, Pan Y, Wu P, Jia Q, Bao Z, Bai L, Jin M, Sumpter B, Fung V, Huang W, Wu Z. Angew Chem Int Ed, 2020, 59: 7969
Hu B, Zhang X, Mo Y, Li J, Lin LL, Liu X, Feng X. Org Lett, 2020, 22: 1034–1039
Dong P, Chen L, Yang Z, Dong S, Feng X. Org Chem Front, 2021, 8: 6874–6880
Xu C, Qiao J, Dong S, Zhou Y, Liu X, Feng X. Chem Sci, 2021, 12: 5458–5463
Wang K, Xu C, Hu X, Zhou Y, Lin L, Feng X. Chem Commun, 2021, 57: 8917–8920
Lang J, Wang S, He C, Liu X, Feng X. Chem Sci, 2022, 13: 1163–1168
Liu Y, Chen Y, Yihuo A, Zhou Y, Liu X, Lin L, Feng X. ACS Catal, 2022, 12: 1784–1790
Wang H, Xu Y, Zhang F, Liu Y, Feng X. Angew Chem Int Ed, 2022, 61: e202115715
Wang W, Zhang F, Liu Y, Feng X. Angew Chem Int Ed, 2022, 61: e202208837
Xu Y, Wang HK, Yang Z, Zhou YQ, Liu YB, Feng XM. Chem, 2022, 8: 2011–2022
CCDC 2239244 (C26); (b) CCDC 2240471 (E3); (c) CCDC 2257114 (E12)
Singh IP, Milligan KE, Gerwick WH. J Nat Prod, 1999, 62: 1333–1335
Carda M, Rodrıguez S, Castillo E, Bellido A, Dıaz-Oltra S, Alberto Marco J. Tetrahedron, 2003, 59: 857–864
Doran R, Duggan L, Singh S, Duffy CD, Guiry PJ. Eur J Org Chem, 2011, 2011: 7097–7106
Jinnouchi H, Nambu H, Fujiwara T, Yakura T. Tetrahedron, 2018, 74: 1059–1070
Liu XH, Lin LL, Feng XM. Acc Chem Res, 2011, 44: 574–587
Liu X, Zheng H, Xia Y, Lin L, Feng X. Acc Chem Res, 2017, 50: 2621–2631
Wang M-, Li W. Chin J Chem, 2021, 39: 969–984
Dong S, Liu X, Feng X. Acc Chem Res, 2022, 55: 415–428
Liu Y, Liu X, Feng X. Chem Sci, 2022, 13: 12290–12308
Chen DF, Gong LZ. Org Chem Front, 2023, 10: 3676–3683
Zhang X, Wu W, Cao W, Yu H, Xu X, Liu X, Feng X. Angew Chem Int Ed, 2020, 59: 4846–4850
Hu X, Tang X, Zhang X, Lin L, Feng X. Nat Commun, 2021, 12: 3012
He C, Wu Z, Zhou Y, Cao W, Feng X. Org Chem Front, 2022, 9: 703–708
Wang Y, Yihuo A, Wang L, Dong S, Feng X. Sci China Chem, 2022, 65: 546–553
Zhan T, Yang L, Chen Q, Weng R, Liu X, Feng X. CCS Chem, 2023, 5: 2101–2110
Wu Z, Zhang X, Xu N, Liu X, Feng X. ACS Catal, 2023, 13: 815–823
Marenich AV, Cramer CJ, Truhlar DG. JPhys Chem B, 2009, 113: 6378–6396
Zhao Y, Schultz NE, Truhlar DG. J Chem Theor Comput, 2006, 2: 364–382
Weigend F, Ahlrichs R. Phys Chem Chem Phys, 2005, 7: 3297–3305
Andrae D, Häußermann U, Dolg M, Stoll H, Preuß H. Theoret Chim Acta, 1990, 77: 123–141
Jensen F. J Chem Theor Comput, 2006, 2: 1360–1369
Grimme S. J Comput Chem, 2006, 27: 1787–1799
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, MontgomeryJr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J. Fox DJ. Gaussian09, Revision D.01. Wallingford, CT: Gaussian, Inc., 2013
Lu T, Chen F. J Comput Chem, 2012, 33: 580–592
Lu T, Chen Q. J Comput Chem, 2022, 43: 539–555
Acknowledgements
This work was supported by the National Natural Science Foundation of China (U19A2014) and Sichuan University (2020SCUNL204). We are grateful to Dr Yuqiao Zhou (Sichuan University) for the X-ray single crystal diffraction analysis.
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Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis
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Chen, M., Yang, L., Li, Y. et al. Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis. Sci. China Chem. 67, 542–550 (2024). https://doi.org/10.1007/s11426-023-1794-2
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DOI: https://doi.org/10.1007/s11426-023-1794-2