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Rhodium-catalyzed deuterioformylation of the ketal-masked β-isophorone: Evidence for a tertiary alkyl rhodium intermediate as a precursor of the main reaction product acetaldehyde derivative

Authors
Journal
Inorganica Chimica Acta
0020-1693
Publisher
Elsevier
Publication Date
Volume
362
Issue
5
Identifiers
DOI: 10.1016/j.ica.2008.07.006
Keywords
  • Deuterioformylation
  • Regioselectivity
  • Tertiary Rhodium Alkyl
  • β-Elimination
  • Isomerization

Abstract

Graphical abstract The rhodium-catalyzed deuterioformylation of the ketal-masked β-isophorone 7,9,9-trimethyl-1,4-dioxa-spiro[4.5]dec-7-ene ( 1) under 100 atm of syngas, at 100 °C, gives the trideuterated acetaldehyde derivative 2 as the main product, originating from a primary alkyl rhodium intermediate c via isomerization of the tertiary one a. Theoretical calculations indicate that secondary and tertiary rhodium alkyl intermediates are formed in a similar amount and hence their evolution to aldehydes occurs with different rates.

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