Palladium Catalyzed Controllable Mono‐ or Di‐Allylic Substitution Reaction of Benzothiazolylacetate with Allylic Alcohols

Abstract

A Pd(PPh 3 ) 4 /acid catalyzed highly efficient and mono-or di-selective allylic substitution reaction of benzothiazolylacetate and allylic alcohols has been developed. The mono-and di-selectivities could be efficiently controlled by changing the reaction solvent and temperature, affording various mono-and diallylated products in good to excellent yields and selectivities. Both linear and branched allylic alcohols as well as allyl alcohol could all be well tolerated in the reaction.

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

“…237 Site selectivity and enantiocontrol was achieved through the use of a chiral Brønsted acid cocatalyst, with the alcohol being activated through CO 2 -mediated formation of a carbonic ester. Other groups have also explored the use of dual palladium/Brønsted acid or palladium/amine catalysis in allylic alkylation reactions of unsaturated carbon compounds using alcohol substrates, including as Gong, 238 Zhang, 239 Reek, 240 Jiang, 241,242 Luo, 243 Zhang, 244 Yoshida, 245 Zhong, 246 and Bica-Schroder (Scheme 38b). 247 In each case, the products of asymmetric allylic alkylation using enol-or enamine-type nucleophiles were observed.…”

Pd-Catalyzed Dearomative Asymmetric Allylic Alkylation of Naphthols with Alkoxyallenes

“…Numerous soft and hard nucleophiles have been involved in this reaction during the last decade. In line with our interest in the development of catalytically asymmetric dearomatic reactions of naphthols and selectivity-controllable allylic substitution reactions, we assumed that an asymmetric metal-catalyzed intermolecular nucleophilic addition reaction to alkoxyallenes involving π-allyl intermediates would be highly suitable for β-naphthols, allowing access to dearomative cyclohexadienone derivatives. Herein, we report the first Pd-catalyzed linear selective asymmetric allylic dearomatization of β-naphthols with alkoxyallenes for the construction of β-naphthalenones bearing an all-carbon quaternary chiral center in good yields and enantioselectivities.…”

Palladium-Catalyzed Allylic Substitution Reaction of Benzothiazolylacetamide with Allylic Alcohols in Water

“…Recently, we reported a palladium-catalyzed mono- or diselective allylic substitution reaction of benzothiazolylacetate and allylic alcohols, affording various mono- and diallylated products in good to excellent yields and selectivities . As a continuation of our efforts in chemoselective allylic substitution reactions, we report herein a palladium-catalyzed highly efficient atom-economic and environmentally friendly allylic substitution reaction of benzathiazole acetic amides with allylic alcohols by using H 2 O as the solvent.…”