Mesoionic Carbene (MIC)-Catalyzed H/D Exchange at Formyl Groups
- 주제(기타) Chemistry, Multidisciplinary
- 등재 SCIE, SCOPUS
- OA유형 Bronze
- 발행기관 CELL PRESS
- 발행년도 2019
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000161456
- 본문언어 영어
- Published As http://dx.doi.org/10.1016/j.chempr.2019.08.011
초록/요약
H/D exchange at formyl groups is the most direct approach for the synthesis of deuterated aldehydes. Platinum-group metal complexes have been employed to catalyze this transformation, with significant substrate scope limitations. Although N-heterocyclic carbenes can also activate the C- H bond of aldehydes through the formation of Breslow intermediates, benzoin condensation and other C-C-bond-forming pathways have so far outpaced synthetically useful H/D exchange. Investigation of the reaction of aldehydes with 1,2,3-triazolylidenes has revealed the reversible formation of Breslow intermediates and the inhibition of the condensation steps in methanol solvent. 1,2,3-Triazolylidenes catalyze the H/D exchange of aryl, alkenyl, and alkyl aldehydes in high yields and deuterium incorporation levels using deuterated methanol as an affordable D source. The unique properties of these mesoionic carbenes (MICs) enable a streamlined preparation of deuterated synthetic intermediates and pharmaco-phores that are highly valuable as mechanistic and metabolic probes.
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