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

Mahshid Yaghoubi; Isabella C. Reyes; Benjamin J. Stokes

doi:10.1055/a-2367-6943

SynOpen, Table of Contents

CC BY 4.0 · SynOpen 2024; 08(03): 169-172
DOI: 10.1055/a-2367-6943

letter

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

Authors

Mahshid Yaghoubi

^aDepartment of Chemistry and Chemical Biology, University of California, Merced, 5200 N. Lake Road, Merced, CA 95343, USA
Isabella C. Reyes

^bDepartment of Chemistry and Biochemistry, Santa Clara University, 500 El Camino Real, Santa Clara, CA 95053, USA
Benjamin J. Stokes ∗

^bDepartment of Chemistry and Biochemistry, Santa Clara University, 500 El Camino Real, Santa Clara, CA 95053, USA

Abstract

All articles of this category

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

Full Text

References

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

Supplementary Material

Supporting Information (PDF)