A Sequential Homologation of Alkynes and Aldehydes for Chain Elongation with Optional (13) C-Labeling

Chemistry : a European Journal
Andreas Brunner, Lukas Hintermann

Abstract

Terminal alkynes (RCCH) are homologated by a sequence of ruthenium-catalyzed anti-Markovnikov hydration of alkyne to aldehyde (RCH2 CHO), followed by Bestmann-Ohira alkynylation of aldehyde to chain-elongated alkyne (RCH2 CCH). Inverting the sequence by starting from aldehyde brings about the reciprocal homologation of aldehydes instead. The use of (13) C-labeled Bestmann-Ohira reagent (dimethyl ((1-(13) C)-1-diazo-2-oxopropyl)phosphonate) for alkynylation provides straightforward access to singly or, through additional homologation, multiply (13) C-labeled alkynes. The labeled alkynes serve as synthetic platform for accessing a multitude of specifically (13) C-labeled products. Terminal alkynes with one or two (13) C-labels in the alkyne unit have been submitted to alkyne-azide click reactions; the copper-catalyzed version (CuAAC) was found to display a regioselectivity of >50 000:1 for the 1,4- over the 1,5-triazine isomer, as shown analytically by (13) C NMR spectroscopy.

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Citations

Aug 27, 2016·The Journal of Organic Chemistry·Juliane Adrian, Christian B W Stark
May 3, 2020·Nature Communications·Kazunori MiyamotoMasanobu Uchiyama

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