Pd-Catalyzed Transfer Hydrogenation of Alkenes Using Tetrahydroxydiboron as the Sole Hydrogen Donor

Abstract

Tetrahydroxydiboron-mediated catalytic transfer hydrogenations have typically involved co-additives that, like tetrahydroxydiboron itself, are H atom donors. Herein we report an alkene transfer hydrogenation method with tetrahydroxydiboron as the sole source of H atoms. The reaction uses Pd(OAc)₂ as a convenient putative colloid pre-catalyst, and cyclic monoethers are competent solvents. Highly efficient alkene deuteration is demonstrated using tetradeuteroxydiboron.

Key words

tetrahydroxydiboron - transfer hydrogenation - palladium catalysis - alkene reduction - deuterium - catalytic hydrogenation

Publikationsverlauf

Eingereicht: 06. Juni 2024

Angenommen nach Revision: 03. Juli 2024

Accepted Manuscript online:
16. Juli 2024

Artikel online veröffentlicht:
14. August 2024

• References and Notes

• 1a Brieger G, Nestrick TJ. Chem. Rev. 1974; 74: 567
• 1b Zassinovich G, Mestroni G, Gladiali S. Chem. Rev. 1992; 92: 1051
• 2 Wang D, Astruct D. Chem. Rev. 2015; 115: 6621
• 3 Broggi J, Jurčík M, Songis O, Poater A, Cavallo LA. M. Z. Slawin A. M. Z, Cazin CS. J. J. Am. Chem. Soc. 2013; 135: 4588
• 4a Wang Y, Huang Z, Leng X, Zhu H, Liu G, Haung Z. J. Am. Chem. Soc. 2018; 140: 4417
• 4b Bao H, Zhou B, Jin H, Liu Y. J. Org. Chem. 2019; 84: 3579
• 5 Staubitz A, Robertson AP. M, Manners I. Chem. Rev. 2010; 110: 4079

For a relevant example using a disilane, see:
• 6a Shirakawa E, Otsuka H, Hayashi T. Chem. Commun. 2005; 5885

Leading examples employing R₃SH reagents:
• 6b Luo F, Pan C, Wang W, Ye Z, Cheng J. Tetrahedron 2010; 66: 1399
• 6c Wang G, Bin H, Sun M, Chen S, Liu J, Zhong C. Tetrahedron 2014; 70: 2175

Examples employing polymeric silanes:
• 6d Volkov A, Gustafson KP. J, Tai C.-W, Verho O, Bäckvall JE, Adolfsson H. Angew. Chem. Int. Ed. 2015; 54: 5122
• 6e Rahaim RJ, Maleczka RE. Org. Lett. 2011; 13: 584
• 6f Dal Zotto C, Virieux D, Campagne JM. Synlett 2009; 276
• 6g Argouarch G. New J. Chem. 2019; 43: 11041

For examples using water, see:
• 7a Cummings SP, Le T.-N, Fernandez GE, Quiambao LG, Stokes BJ. J. Am. Chem. Soc. 2016; 138: 6107
• 7b Zhou Y, Zhou H, Liu S, Pi D, Shen G. Tetrahedron 2017; 73: 3898
• 7c Rao S, Prabhu KL. Chem. Eur. J. 2018; 24: 13954
• 7d Gates AM, Santos WL. Synthesis 2019; 51: 4619
• 7e Zhang K, Okumura S, Uozumi Y. Chem. Lett. 2024; 53: upae082
• 7f Zhang K, Okumura S, Uozumi Y. Eur. J. Org. Chem. 2024; 27: e202400322
• 7g Alghamdi HS, Ajeebi AF, Aziz MA, Alzahrani AS, Shaikh MN. ACS Omega 2024; 9: 11377

For a homogeneous nickel-catalyzed asymmetric variant using hexafluoroisoproanol, see:
• 7h Wu B, Bai Y.-Q, Wang X.-Q, Huang W.-J, Zhou Y.-G. J. Org. Chem. 2024; 89: 710

For a review of tetrahydroxydiboron in synthesis, see:
• 8a Zhao Q, Liu X, Astruc D. Eur. J. Inorg. Chem. 2023; 26: e202300024

For a review of B₂(OR)₄ reagents in organic synthesis, see:
• 8b Neeve EC, Geier SJ, Mkhalid IA. I, Westcott SA, Marder TB. Chem. Rev. 2016; 116: 9091

For a review of metal-free H₂-evolving hydrolysis of B₂(OH)₄, see:
• 8c Liu X, Zhang X, Zhang G, Sun S, Li D.-S. ACS Mater. Lett. 2023; 5: 783

For leading examples of Miyaura borylation using B₂(OH)₄, see:
• 8d Raducan M, Alam R, Szabó KJ. Angew. Chem. Int. Ed. 2012; 51: 13050
• 8e Molander GA, Trice SL. J, Kennedy SM, Dreher SD, Tudge MT. J. Am. Chem. Soc. 2012; 134: 11667
• 9a Gurung SR, Mitchell C, Huang J, Jonas M, Strawser JD, Daia E, Hardy A, O’Brien E, Hicks F, Papageorgiou CD. Org. Process Res. Dev. 2017; 21: 65
• 9b Williams MJ, Chen Q, Codan L, Dermenjian RK, Dreher S, Gibson AW, He X, Jin Y, Keen SP, Lee AY, Lieberman DR, Lin W, Liu G, McLaughlin M, Reibarkh M, Scott JP, Strickfuss S, Tan L, Varsolona RJ, Wen F. Org. Process Res. Dev. 2016; 20: 1227

For a nickel-catalyzed variant, see:
• 9c Coombs JR, Green RA, Roberts F, Simmons EM, Stevens JM, Wisniewski SR. Organometallics 2019; 38: 157

For safety concerns surrounding H₂ generation in transition-metal-catalyzed Miyaura borylations on industrial scale, see:
• 9d Merritt JM, Borkar I, Buser JY, Campbell Brewer A, Campos O, Fleming J, Hansen C, Humenik A, Jefferey S, Kokitkar PB, Kolis SP, Forst MB, Lambertus GR, Martinelli JR, McCartan C, Moursy H, Murphy D, Murray MM, O’Donnell K, O’Sullivan R, Richardson GA, Xia H. Org. Process Res. Dev. 2022; 26: 773
• 10 Korvinson KA, Akula HK, Malinchak CT, Sebastian D, Wei W, Khandaker TA, Andrzejewska MR, Zajc B, Lakshman MK. Adv. Synth. Catal. 2020; 362: 166
• 11 Spaller WC, Lu JQ, Stokes BJ. Adv. Synth. Catal. 2022; 364: 2571
• 12 See the Supporting Information for details.
• 13 Metaboric acid is the product of β-hydride elimination of [M]–B(OH)₂. For an example of tetrahydroxydiboron-mediated copper-catalyzed reduction of azaarenes and nitroarenes invoking metaboric acid as a byproduct, see: Pi D, Zhou H, Zhou Y, Liu Q, He R, Shen G, Uozumi Y. Tetrahedron 2018; 74: 2121
• 14a Elmore CS, Bragg RA. Bioorg. Med. Chem. Lett. 2015; 25: 167
• 14b Gant TG. J. Med. Chem. 2014; 57: 3595
• 15 Baldwin RM. J. Nucl. Med. 2005; 46: 1411
• 16a Schramm VL. Chem. Biol. 2007; 11: 529
• 16b Scheppele SE. Chem. Rev. 1972; 72: 511
• 17a Bell RP. Chem. Soc. Rev. 1974; 3: 513
• 17b Wiberg KB. Chem. Rev. 1955; 55: 713
• 18 Simmons EM, Hartwig JF. Angew. Chem. Int. Ed. 2012; 51: 3066

For background on the interpretation of mercury poisoning control experiments, see:
• 19a Weddle KS, Aiken JD, Finke RG. J. Am. Chem. Soc. 1998; 120: 5653
• 19b Widegren JA, Finke RG. J. Mol. Catal. A: Chem. 2003; 198: 317
• 20 General Transfer Hydrogenation Procedure An oven-dried one-dram disposable borosilicate vial is charged with a magnetic stir bar, 58.3 mg of tetrahydroxydiboron (0.65 mmol, 1.3 equiv), 2.3 mg of Pd(OAc)₂ (0.01 mmol, 0.02 equiv), and substrate if solid (0.5 mmol, 1.0 equiv). The vial is capped and purged with argon or nitrogen gas, then charged with 1.7 mL of degassed anhydrous THF and heated to 60 °C for 6 h with stirring at 600 rpm. After cooling to ambient temperature, the solution is filtered through a plug of silica gel and rinsed with dichloromethane.
• 21 Characterization Data of Representative Product 2a Yield (0.5 mmol scale): 88 mg (97%), colorless solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.29–7.25 (m, 4 H), 7.21–7.16 (m, 6 H), 2.92 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 142.1, 128.6, 128.4, 126.0, 38.0.
• 22 A version of this manuscript was deposited on ChemRxiv prior to review: Yaghoubi M, Reyes IC, Stokes BJ. ChemRxiv 2024; preprint