Synlett 2020; 31(07): 699-702
DOI: 10.1055/s-0040-1707993
letter
© Georg Thieme Verlag Stuttgart · New York

N-Heterocyclic Carbene Catalyzed Deuteration of Aldehydes in D2O

Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan   eMail: sawama@gifu-pu.ac.jp   eMail: sajiki@gifu-pu.ac.jp
,
Yuya Miki
,
Hironao Sajiki
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan   eMail: sawama@gifu-pu.ac.jp   eMail: sajiki@gifu-pu.ac.jp
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Publikationsverlauf

Received: 02. Dezember 2019

Accepted after revision: 08. Januar 2020

Publikationsdatum:
03. März 2020 (online)


Abstract

An N-heterocyclic carbene (NHC)-catalyzed direct deuteration of aldehydes in a mixed solvent of deuterium oxide (D2O) and cyclopentyl methyl ether was established. The present deuteration is possibly initiated by the formation of a Breslow intermediate from the aldehyde and the NHC, with subsequent trapping by D2O providing the monodeuterated aldehyde.

Supporting Information

 
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  • 14 Monodeuterated Aldehydes 1a-d 1 to 1n-d 1; General Procedure An 18 mL test tube was charged with the appropriate aldehyde (0.2 mmol), IMes·HCl (6.8 mg, 0.02 mmol), Na2CO3 (4.2 mg, 0.04 mmol), CPME (0.2 mL), and D2O (1.0 mL). The tube was then sealed with a septum and the gas inside the tube was immediately replaced with Ar. The mixture was then heated at 120 °C for the appropriate time (Table 3), then extracted with EtOAc. The organic layers were dried (MgSO4) and concentrated in vacuo. If necessary, the residue was purified by column chromatography (silica gel). 4-Methoxybenzaldehyde-d 1 (1a-d 1 ): Yield: 15.8 mg (58%; 99% D incorporation). 1H NMR (400 MHz, CDCl3): δ = 9.88 (s, 0.01 H), 7.84 (d, J = 8.2 Hz, 2 H), 7.00 (d, J = 8.2 Hz, 2 H), 3.89 (s, 3 H). 2H NMR (77 MHz, CHCl3): δ = 9.91 (br s).
  • 15 Because of the volatility of the aldehyde products, yields were determined by 1H NMR with CH2Br2 as an internal standard, unless otherwise noted.