Nickel-Catalyzed Regiodivergent Reductive Hydroarylation of Styrenes

Abstract

We report a ligand-controlled nickel-catalyzed reductive hydroarylation of styrenes with predictable and controllable regioselectivity. With a diamine ligand, the reaction produces selective linear hydroarylation products. Alternatively, with a chiral PyrOx ligand, branch-selective enantioenriched 1,1-diarylalkane products are obtained. Preliminary mechanistic results are consistent with a reductive Heck process.

Key words

asymmetric catalysis - hydroarylation - nickel catalysis - reductive Heck - regiodivergence - styrene

• References and Notes


For NiH-catalyzed branched redox-neutral hydroarylation of styrenes, see:
• 1a Xiao L.-J, Cheng L, Feng W.-M, Li M.-L, Xie J.-H, Zhou Q.-L. Angew. Chem. Int. Ed. 2018; 57: 461
• 1b Chen Y.-G, Shuai B, Xu X.-TLi Y.-Q, Yang Q.-L, Qiu H, Zhang K, Fang P, Mei T.-S. J. Am. Chem. Soc. 2019; 141: 3395
• 1c Lv X.-Y, Fan C, Xiao L.-J, Xie J.-H, Zhou Q.-L. CCS Chem. 2019; 1: 328
• 1d He Y, Liu C, Yu L, Zhu S. Angew. Chem. Int. Ed. 2020; 59: 9186
• 1e Tran HN, Burgett RW, Stanley LM. J. Org. Chem. 2021; 86: 3836

For PdH-catalyzed branched redox-neutral hydroarylation of styrenes, see:
• 1f Iwai Y, Gligorich KM, Sigman MS. Angew. Chem. Int. Ed. 2008; 47: 3219
• 1g Podhajsky SM, Iwai Y, Cook-Sneathen A, Sigman MS. Tetrahedron 2011; 67: 4435

For NiH-catalyzed branched reductive hydroarylation of styrenes, see:
• 2a He Y, Cai Y, Zhu S. J. Am. Chem. Soc. 2017; 139: 1061
• 2b Chen F, Chen K, Zhang Y, He Y, Wang Y.-M, Zhu S. J. Am. Chem. Soc. 2017; 139: 13929
• 2c Kumar GS, Peshkov A, Brzozowska A, Nikolaienko P, Zhu C, Rueping M. Angew. Chem. Int. Ed. 2020; 59: 6513
• 2d He Y, Liu C, Yu L, Zhu S. Angew. Chem. Int. Ed. 2020; 59: 21530

For CuH-catalyzed branched reductive hydroarylation of styrenes, see:
• 2e Semba K, Ariyama K, Zheng H, Kameyama R, Sakaki S, Nakao Y. Angew. Chem. Int. Ed. 2016; 55: 6275
• 2f Friis SD, Pirnot MT, Buchwald SL. J. Am. Chem. Soc. 2016; 138: 8372
• 3a Messaoudi S, Hamze A, Provot O, Tréguier B, Rodrigo De Losada J, Bignon J, Liu J.-M, Wdzieczak-Bakala J, Thoret S, Dubois J, Brion J.-D, Alami M. ChemMedChem 2011; 6: 488
• 3b Moree WJ, Li B.-F, Jovic F, Coon T, Yu J, Gross RS, Tucci F, Marinkovic D, Zamani-Kord S, Malany S, Bradbury MJ, Hernandez LM, O’Brien Z, Wen J, Wang H, Hoare SR. J, Petroski RE, Sacaan A, Madan A, Crowe PD, Beaton G. J. Med. Chem. 2009; 52: 5307
• 3c Chubb NA. L, Cox MR, Dauvergne JS, Ewin RA, Lauret C. US 20070167506, 2007

For selected reviews on metal-hydride chemistry, see:
• 4a Pirnot MT, Wang Y.-M, Buchwald SL. Angew. Chem. Int. Ed. 2016; 55: 48
• 4b Nguyen KD, Park BY, Luong T, Sato H, Garza VJ, Krische MJ. Science 2016; 354: 300
• 4c Eberhardt NA, Guan H. Chem. Rev. 2016; 116: 8373
• 4d Crossley SW. M, Obradors C, Martinez RM, Shenvi RA. Chem. Rev. 2016; 116: 8912
• 4e Chen J, Guo J, Lu Z. Chin. J. Chem. 2018; 36: 1075
• 4f Wang X.-X, Lu X, Li Y, Wang J.-W, Fu Y. Sci. China: Chem. 2020; 63: 1586

For Ni-catalyzed reductive Heck reaction, see:
• 5a Qin X, Lee MW. Y, Zhou JS. Angew. Chem. Int. Ed. 2017; 56: 12723
• 5b Yang F, Jin Y, Wang C. Org. Lett. 2019; 21: 6989
• 5c Huang X, Teng S, Chi YR, Xu W, Pu M, Wu Y.-D, Zhou JS. Angew. Chem. Int. Ed. 2021; 60: 2828

For selected reviews on nickel catalysis, see:
• 6a Netherton MR, Fu GC. Adv. Synth. Catal. 2004; 346. 1525
• 6b Hu X. Chem. Sci. 2011; 2: 1867
• 6c Montgomery J. Organonickel Chemistry . In Organometallics in Synthesis . Lipshutz BH. John Wiley & Sons; Hoboken: 2013: 319-428
• 6d Tasker SZ, Standley EA, Jamison TF. Nature 2014; 509: 299
• 6e Nickel Catalysis in Organic Synthesis . Ogoshi S. Wiley-VCH; Weinheim: 2020
• 6f Poremba KE, Dibrell SE, Reisman SE. ACS Catal. 2020; 10: 8237

For NiH-catalyzed branched hydroarylation of unactivated alkenes, see:
• 7a Green SA, Matos JL. M, Yagi A, Shenvi RA. J. Am. Chem. Soc. 2016; 138: 12779
• 7b Shevick SL, Obradors C, Shenvi RA. J. Am. Chem. Soc. 2018; 140: 12056

For NiH-catalyzed branch-selective reductive hydrovinylation of 1,3-dienes, see:
• 7c Pang X, Zhao Z.-Z, Wei X.-X, Qi L, Xu G, Duan J, Liu X.-Y, Shu X.-Z. J. Am. Chem. Soc. 2021; 143: 4536

For other type of NiH-catalyzed asymmetric reductive hydrofunctionalizations, see:
• 8a Wang Z, Yin H, Fu GC. Nature 2018; 563: 379
• 8b He S.-J, Wang J.-W, Li Y, Xu Z.-Y, Wang X.-X, Lu X, Fu Y. J. Am. Chem. Soc. 2020; 142: 214
• 8c Yang Z.-P, Fu GC. J. Am. Chem. Soc. 2020; 142: 5870
• 8d Bera S, Mao R, Hu X. Nat. Chem. 2021; 13: 270
• 8e Liu J, Gong H, Zhu S. Angew. Chem. Int. Ed. 2021; 60: 4060
• 8f Shi L, Xing L.-L, Hu W.-B, Shu W. Angew. Chem. Int. Ed. 2021; 60: 1599
• 8g Cuesta-Galisteo S, Schörgenhumer J, Wei X, Merino E, Nevado C. Angew. Chem. Int. Ed. 2021; 60: 1605
• 8h He Y, Song H, Zhu S. Nat. Commun. 2021; 12: 638
• 8i Qian D, Bera S, Hu X. J. Am. Chem. Soc. 2021; 143: 1959
• 8j Wang J.-W, Li Y, Nie W, Chang Z, Yu Z.-A, Zhao Y.-F, Lu X, Fu Y. Nat. Commun. 2021; 12: 1313
• 8k Wang X.-X, Yu L, Lu X, Zhang Z.-L, Liu D.-G, Tian C, Fu Y. CCS Chem. 2021; 3: 727
• 8l Wang S, Zhang T.-Y, Zhang J.-X, Meng H, Chen B.-H, Shu W. ChemRxiv 2020; preprint
• 8m Jiang X, Han B, Xue Y, Duan M, Gui Z, Wang Y, Zhu S. ChemRxiv 2021; preprint
• 8n Zhou F, Zhu S. ChemRxiv. 2021; preprint

For other type of NiH-catalyzed asymmetric redox-neutral hydrofunctionalizations, see:
• 9a Cheng L, Li M.-M, Xiao L.-J, Xie J.-H, Zhou Q.-L. J. Am. Chem. Soc. 2018; 140: 11627
• 9b Marcum JS, Taylor TR, Meek SJ. Angew. Chem. Int. Ed. 2020; 59: 14070
• 9c Shao W, Besnard C, Guénée L, Mazet C. J. Am. Chem. Soc. 2020; 142: 16486
• 9d Yu R, Rajasekar S, Fang X. Angew. Chem. Int. Ed. 2020; 59: 21436

For NiH-catalyzed linear-selective hydroarylation of alkenes, see:
• 10a Lu X, Xiao B, Zhang Z, Gong T, Su W, Fu Y, Liu L. Nat. Commun. 2016; 7: 11129
• 10b Diesel J, Finogenova AM, Cramer N. J. Am. Chem. Soc. 2018; 140: 4489
• 10c Lv H, Xiao L.-J, Zhao D, Zhou Q.-L. Chem. Sci. 2018; 9: 6839
• 10d Loup J, Müller V, Ghorai D, Ackermann L. Angew. Chem. Int. Ed. 2019; 58: 1749
• 10e Nguyen J, Chong A, Lalic G. Chem. Sci. 2019; 10: 3231
• 10f Zhang W.-B, Yang X.-T, Ma J.-B, Su Z.-M, Shi S.-L. J. Am. Chem. Soc. 2019; 141: 5628
• 10g Saper NI, Ohgi A, Small DW, Seba K, Nakao Y, Hartwig JF. Nat. Chem. 2020; 12: 276
• 10h Wang D.-M, Feng W, Wu Y, Liu T, Wang P. Angew. Chem. Int. Ed. 2020; 59: 20399

For selected examples of Pd-catalyzed linear reductive Heck reaction of styrenes, see:
• 11a Torii S, Tanaka H, Morisaki K. Chem. Lett. 1985; 14: 1353
• 11b Jin L, Qian J, Sun N, Hu B, Shen Z, Hu X. Chem. Commun. 2018; 54: 5752
• 11c Oxtoby LJ, Li Z.-Q, Tran VT, Erbay TG, Deng R, Liu P, Engle KM. Angew. Chem. Int. Ed. 2020; 59: 8885
• 11d Yang X.-W, Li D.-H, Song A.-X, Liu F.-S. J. Org. Chem. 2020; 85: 11750

For Cu-catalyzed linear radical reductive arylation of styrenes, see:
• 11e Zhou F, Hu X, Zhang W, Li C.-J. J. Org. Chem. 2018; 83: 7416

For other selected examples of linear hydroarylation of terminal alkenes, see:
• 12a Friis SD, Pirnot MT, Dupuis LN, Buchwald SL. Angew. Chem. Int. Ed. 2017; 56: 7242
• 12b Boyington AJ, Riu M.-LY, Jui NT. J. Am. Chem. Soc. 2017; 139: 6582
• 12c Lu Z, Buchwald SL. Angew. Chem. Int. Ed. 2020; 59: 16128
• 12d Wang C, Xiao G, Guo T, Ding Y, Wu X, Loh T.-P. J. Am. Chem. Soc. 2018; 140: 9332
• 13 For an elegant example of ligand-controlled regiodivergent hydroarylation of terminal alkenes, see: Li Z.-Q, Fu Y, Deng R, Tran VT, Gao Y, Liu P, Engle KM. Angew. Chem. Int. Ed. 2020; 59: 23306
• 14 1-Methoxy-4-phenethylbenzene (3a) – General Procedure A In a nitrogen-filled glove box, to an oven-dried 8 mL screw-cap vial equipped with a magnetic stir bar were added NiBr₂·3H₂O (2.73 mg, 0.010 mmol, 5 mol%), L1 (2.55 mg, 0.012 mmol, 6 mol%), CsF (60.8 mg, 0.40 mmol, 2.0 equiv), and 0.40 mL anhydrous THF. The mixture was stirred for 5 min, at which time PMHS (30 μL, 0.50 mmol, 2.5 equiv) was added, and the stirring was continued for another 5 min at r.t. Styrene (1a, 31.2 mg, 0.30 mmol, 1.5 equiv) and 4-methoxyphenyl trifluoromethanesulfonate (2a, 51.2 mg, 0.20 mmol, 1.0 equiv) were added to the resulting mixture in this order. The tube was sealed with a Teflon-lined screw cap, removed from the glove box and stirred at 25 °C for up to 24 h. The reaction was quenched upon the addition of H₂O, and the mixture was extracted with EtOAc (3 ×). The organic layer was concentrated to give the crude product. n-Dodecane (20 μL) was added as an internal standard for GC analysis. The product was purified by chromatography on silica gel for each substrate. The crude material was purified by flash column chromatography (PE–EtOAc = 100:1) to provide the title compound as a white solid in 85% yield (36.0 mg). The analytical data are consistent with values reported in the literature.^10e
• 15 (S)-1-Methoxy-4-(1-phenylethyl)benzene (4a) – General Procedure B In a nitrogen-filled glove box, to an oven-dried 8 mL screw-cap vial equipped with a magnetic stir bar were added NiCl₂·glyme (2.20 mg, 0.010 mmol, 5 mol%), L4 (4.27 mg, 0.012 mmol, 6 mol%), K₃PO₄·H₂O (92.1 mg, 0.40 mmol, 2.0 equiv), methanol (3.2 mg, 0.10 mmol, 0.5 equiv), and mixed solvent (Et₂O–toluene = 3:1, 0.40 mL). The reaction mixture was stirred for 5 min, at which time PMHS (30 μL, 0.50 mmol, 2.5 equiv) was added, and the stirring was continued for another 5 min at r.t. Styrene (1a, 31.2 mg, 0.30 mmol, 1.5 equiv) and 4-methoxyphenyl trifluoromethanesulfonate (2a, 51.2 mg, 0.20 mmol, 1.0 equiv) were added to the resulting mixture in this order. The tube was sealed with a Teflon-lined screw cap, removed from the glove box and stirred at 0 °C for up to 24 h. The reaction was quenched upon the addition of H₂O, and the mixture was extracted with EtOAc (3 ×). The organic layer was concentrated to give the crude product. n-Dodecane (20 μL) was added as an internal standard for GC analysis. The crude material was purified by flash column chromatography (PE–EtOAc = 100:1) to provide the title compound as a colorless oil in 55% yield (23.3 mg), 94:6 rr. HPLC analysis (OJ-H, 5% ⁱ PrOH/hexane, 1.0 mL/min, 220 nm) indicated 95% ee, t _R (major) = 16.9 min, t _R (minor) = 18.1 min. The analytical data are consistent with values reported in the literature.^2f
• 16 Under branch-selective reaction conditions, when (Bpin)₂ was used instead of PMHS, the regioreversed arylboration product was obtained in 36% yield, 94:6 rr, 94% ee.
• 17 For similar Heck-type reaction, see: Chen L.-A, Lear AR, Gao P, Brown MK. Angew. Chem. Int. Ed. 2019; 58: 10956