Rhodium-catalyzed C–H activation and conjugate addition under mild conditions

Abstract

An efficient rhodium(III)-catalyzed C-H activation and subsequent conjugate addition was achieved under mild conditions. The reaction utilized inert arenes to replace stoichiometric organometallic reagents and can tolerate various functional groups as well as air and water.

Brønsted Acid Enhanced Rhodium‐Catalyzed Conjugate Addition of Aryl CH Bonds to α,β‐Unsaturated Ketones under Mild Conditions

“…Benzalacetones showed a high compatibility with the present reaction conditions, affording the desired products ( 3 ap , 3 aq , and 3 ar ) in good yields. It was noteworthy that the Michael acceptors could be extended to aliphatic α,β‐unsaturated ketones, to give the products in excellent yields at room temperature 11. The substrate scope of arenes was then investigated.…”

“…It was noteworthy that the Michael acceptors could be extended to aliphatic a,b-unsaturated ketones, to give the products in excellent yields at room temperature. [11] The substrate scope of arenes was then investigated. To our satisfaction, both para-substituted electron-rich and electron-deficient arylpyridine derivatives (1 b, 1 c, 1 d, and 1 e) worked well with 2 a, and gave the desired products 3 ba, 3 ca, 3 da, and 3 ea in good to excellent yields.…”

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

“…Recently, Bergman [136] and Shi [137] et al reported the rhodium-catalyzed nucleophilic addition of phenylpyridine to Boc and Ts aldimine derivatives respectively. Independently, we reported the aldehyde addition [138] and conjugate addition [139] of protection free substrates catalyzed by rhodium in the presence of water. The most challenging nucleophilic addition via C-H reaction is with simple alkanes.…”

Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds

“…[24] Aconceivable route to the indanone product involves the intramolecular substitution of the hydroxy group by the rhodium enolate,followed by reductive elimination of an acyl indanone.Such compounds are known to undergo retro-Claisen deacylations in the presence of various Lewis acids. [24] Aconceivable route to the indanone product involves the intramolecular substitution of the hydroxy group by the rhodium enolate,followed by reductive elimination of an acyl indanone.Such compounds are known to undergo retro-Claisen deacylations in the presence of various Lewis acids.…”