Developments in the Photochemistry of Diazo Compounds

Nuno R. Candeias, Carlos A. M. Afonso

Research output: Contribution to journalLiterature reviewScientificpeer-review

82 Citations (Scopus)
1194 Downloads (Pure)

Abstract

This review focuses on photolytic reactions of diazo compounds, namely aryl-diazo alkanes and alpha-diazo carbonyl compounds, covering their synthetic applications such as Wolff rearrangement, 1,2-shift, X-H insertion, cyclopropanation, hydrogen abstraction and reaction with oxygen as well as physical organic studies, with special relevance to mechanistic considerations. Singlet-triplet gap studies and the solvent influence on the stability and reactivity of carbenes are also covered together in this review to provide a comprehensive interpretation of their reactivity. The mechanism of the synthetically important Wolff rearrangement, which remains to this day open to dicussion, is evaluated in terms of the role of the diazo framework. 1,2-Shift photoinduced reactions, on the other hand, present well established mechanisms due to recent studies that have demonstrated the importance of photoexcited diazo species. The cyclopropanation reaction mechanism, which is used to demonstrate the spin multiplicity nature of a free carbene, is also well established. Contrary to these latter cases, O-H insertion and C-H insertion reactions continue to lack defined mechanisms inspite of recent studies. The few examples of diazo compounds reactions with molecular oxygen and hydrogen abstraction present in the literature are also covered.

Original languageEnglish
Pages (from-to)763-787
Number of pages25
JournalCurrent Organic Chemistry
Volume13
Issue number7
DOIs
Publication statusPublished - May 2009
Externally publishedYes
Publication typeA1 Journal article-refereed

Keywords

  • LASER-FLASH-PHOTOLYSIS
  • ALPHA-DIAZOCARBONYL COMPOUNDS
  • C-H ACTIVATION
  • PHOSPHONATE GROUP PARTICIPATION
  • TRIPLET ENERGY-GAP
  • WOLFF REARRANGEMENT
  • O-H
  • SUBSTITUTED CARBENES
  • RHODIUM CARBENOIDS
  • CARBONYL-COMPOUNDS

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