A Novel Palladium-Catalyzed Arylation−Dehydroaromatization Reaction:  Synthesis of 7-Aryltetralones

Abstract

A new one-pot room-temperature palladium-catalyzed synthesis of 7-aryltetralones was discovered. This tandem process includes a palladium-catalyzed gamma-selective arylation of the enone 4 followed by a dehydrogenation-aromatization of the initial cross-coupling product. [reaction: see text]

Transition metals in organic synthesis: Highlights for the year 2005

“…(18) Palladium catalyzed an interesting ␥-alkylation-aromatization of bicyclic enones to give 7-aryltetralones (Eq. (19)) [367]. Both C-and O-alkylation was observed upon arylation of 6,8-dimethoxybenzofuran-3-one [368].…”

“…(367)) [1488], the functionalized taxoid ABC-ring system [1514], (−)-malyngolide [756], the C22-C36 subunit of halichondrin B [654], the EF-ring segment of ciguatoxin CTX1B [599] and a laulimalide analog [921]. (367) A number of synthetic applications of the palladiumcatalyzed formation of ␣,␤-unsaturated carbonyl compounds from silylenol ethers (Saegusa oxidation) were published. For example, applications toward kainoids [1515], gymnocin A [205], fumagalone analogs [503], guanacastepenes [1516], GKK1032s [138,1517], the ABCD ring system of manzamine [1176], xestobergsterol A [1518] and (+)-solanascone, (+)-dehydrosolanascone, and (+)-anhydro-␤-rotunol [1519] were described.…”

Palladium‐Catalyzed γ‐Arylation of α,β‐Unsaturated Esters from Silyl Ketene Acetals

“…Martin and Buchwald reported the γ‐arylation of similar α‐substituted α,β‐unsaturated aldehydes 4. Varseev and Maier later reported a sequential γ‐arylation and dehydrogenation for the synthesis of substituted tetralones 5. Finally, Hyde and Buchwald reported the γ‐arylation of γ‐substituted α,β‐ or β,γ‐unsaturated ketones6 and lactones7 with aryl chlorides and bromides in moderate to good yield.…”

Fused Benzo[b]fluorenols: Palladium‐Catalyzed Intramolecular Dehydroaromatization and Carbonyl Reduction

“…[5] Maier demonstrated the convenient synthesis of 7-aryltetralones using a novel arylation-dehydroaromatization sequence. [6] Beckhaus described the dehydroaromatization of quinoxalines through three-fold dehydrogenative C À C coupling. [7] Carbonyl reduction has become increasingly involved in biological systems in which the reduction of a ketone leads to secondary alcohol.…”