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Ruthenium‐Catalyzed Regioselective Cyclization of Aromatic Ketones with Alkynes: An Efficient Route to Indenols and Benzofulvenes
Author(s) -
Chinnagolla Ravi Kiran,
Jeganmohan Masilamani
Publication year - 2012
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201101364
Subject(s) - chemistry , diphenylacetylene , regioselectivity , medicinal chemistry , propyne , trimethylsilyl , alkyne , enyne , ruthenium , catalysis , acetylene , paraformaldehyde , organic chemistry
The reactions of substituted acetophenones with diphenylacetylene in the presence of [{RuCl 2 ( p ‐cymene)} 2 ] (2 mol‐%), AgSbF 6 (8 mol‐%), and Cu(OAc) 2 · H 2 O (25 mol‐%) in 1,2‐dichloroethane at 120 °C for 10 h provided substituted indenol derivatives in good‐to‐excellent yields. Under similar reaction conditions, unsymmetrical alkynes such as 1‐phenyl‐1‐propyne, 1‐phenyl‐1‐butyne, 1‐phenyl‐2‐(trimethylsilyl)acetylene, and a substituted enyne also reacted efficiently with substituted acetophenones to afford the corresponding indenol derivatives in a highly regioselective manner. The amount of silver salt plays a key role in the reaction. When the amount of silver salt exceeded more than 8 mol‐% in the presence of 2 mol‐% [{RuCl 2 ( p ‐cymene)} 2 ], a different type of dehydration product, namely a benzofulvene derivative, started to appear. In the presence of 20 mol‐% AgSbF 6 , substituted acetophenones readily reacted with alkynes in the presence of [{RuCl 2 ( p ‐cymene)} 2 ] (2 mol‐%) to give benzofulvene derivatives in excellent yields. A plausible reaction mechanism is proposed to account for the cyclization reaction.