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CC BY 4.0 · SynOpen 2024; 08(03): 169-172
DOI: 10.1055/a-2367-6943
DOI: 10.1055/a-2367-6943
letter
Pd-Catalyzed Transfer Hydrogenation of Alkenes Using Tetrahydroxydiboron as the Sole Hydrogen Donor
This research was supported by Santa Clara University, the Clare Boothe Luce Program at Santa Clara University (undergraduate research award to I.C.R.), and the University of California Merced.
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 hydrogenationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2367-6943.
- Supporting Information
Publication History
Received: 06 June 2024
Accepted after revision: 03 July 2024
Accepted Manuscript online:
16 July 2024
Article published online:
14 August 2024
© 2024. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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- 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
For a relevant example using a disilane, see:
Leading examples employing R3SH reagents:
Examples employing polymeric silanes:
For examples using water, see:
For a homogeneous nickel-catalyzed asymmetric variant using hexafluoroisoproanol, see:
For a review of tetrahydroxydiboron in synthesis, see:
For a review of B2(OR)4 reagents in organic synthesis, see:
For a review of metal-free H2-evolving hydrolysis of B2(OH)4, see:
For leading examples of Miyaura borylation using B2(OH)4, see:
For a nickel-catalyzed variant, see:
For safety concerns surrounding H2 generation in transition-metal-catalyzed Miyaura borylations on industrial scale, see:
For background on the interpretation of mercury poisoning control experiments, see: