Diverse strategies toward indenol and fulvene derivatives: Rh-catalyzed C-H activation of aryl ketones followed by coupling with internal alkynes

Journal of the American Chemical Society

Volumn 133, Issue 7, 2011, Pages 2154-2156

  Patureau, Frederic W ^a   Besset, Tatiana ^a   Kuhl, Nadine ^a   Glorius, Frank ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARYL KETONES; C-H ACTIVATION; CH-BOND ACTIVATION; FULVENE; FUNCTIONALIZED; INDENOLES; INTERNAL ALKYNES;

ACETYLENE; ACTIVATION ANALYSIS; KETONES; ORGANIC COMPOUNDS; RHODIUM;

CATALYSIS;

ALKYNE DERIVATIVE; CARBON; HYDROGEN; KETONE DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CYCLIZATION; SYNTHESIS;

ALKYNES; CATALYSIS; CYCLOPENTANES; INDENES; KETONES; MOLECULAR STRUCTURE; RHODIUM;

EID: 79951832272     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja110650m     Document Type: Article

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48. Combining α- and γ-strategies did not work out well under our conditions: (Chemical Equation Presented)
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50. 2 (decomposition) did not lead to the expected products.
51. 6 to our optimized conditions led to neither the corresponding indenol 6 nor to fulvene 7, leaving mostly unreacted starting material. This indicates that 5 is not an intermediate of the reaction, thus excluding a Friedel- Crafts-type electrophilic cyclization mechanism. (Chemical Equation Presented)
52. Nevertheless, an indication that the electrophilic cyclization is a critical step in the reaction can be deduced from the fact that 4-methoxyacetophenone and 4-methylacetophenone (poorly electrophilic phenones) yield only 9% and 26%, respectively (2i,j), whereas analogous 3-methylacetophenone yields 68% of the expected α dehydrated product (2e,f). (Chemical Equation Presented)