Direct substitution of the hydroxy group with highly functionalized nitrogen nucleophiles catalyzed by Au(iii)

Abstract

A direct catalytic substitution of various allylic and benzylic alcohols with synthetically useful, but acid-sensitive Boc, Bus, and Dios protected amine nucleophiles, which have not been well utilized for Lewis acid catalysis, with various functionalities (OTBS, OTHP, etc.) was efficiently catalyzed by 1 mol% of Au(III) under mild conditions.

Oxovanadium(V)‐Catalyzed Direct Amination of Allyl Alcohols

“…At 100 °C, the catalytic direct amination reaction of 2 f proceeded regioselectively to give the allyl amine 3 ae in 81 % yield by using 200 mol % of 2 f . The regioselective conversion to α‐methyl cinnamylamine has been also observed in the catalytic reaction of 2 e or 2 f ,,. Isomerization reaction of the allyl amine 3 af was demonstrated to generate the regioisomer 3 ae in 37 % yield (Scheme ), indicating that the generated allyl amine 3 af has the capability to be converted to the allyl amine 3 ae under the reaction conditions.…”

Mechanistic Studies for Synthesis of Bis(indolyl)methanes: Pd-Catalyzed C–H Activation of Indole–Carboxylic Acids with Benzyl Alcohols in Water

“…Recently, direct application of benzyl alcohols as electrophiles in various reactions was achieved via Brønsted/Lewis acid [10][11][12], transition metal [13,14] or water-promoted [15][16][17] We have developed a unique strategy for benzylation and C-H activation [18][19][20][21][22][23][24] by the (η 3 -benzyl)palladium system from a palladium catalyst and benzyl alcohol in water [25][26][27][28]. Water activates the benzyl alcohol via hydration of the hydroxyl group for generation of the (η 3 -benzyl)palladium species, which can then undergo innovative direct transformation reactions.…”

Direct Use of Benzylic Alcohols for Gold(III)‐Catalyzed S‐Benzylation of Mercaptobenzoic Acids in Water

“…Campagne et al reported the nucleophilic substitution of propargylic alcohols by ag old(III) catalyst, which acted as ap ropargylic alcohol-activating agent through coordination to a pbond. [4] Although the direct substitution of benzylic alcohols benefits from high atom and step economies, further progress is needed to develop more environmentally friendly conditions.W ater can be an attractive tool for new transitionm etal-catalyzed reactions. [3] Ohshima andM ashima reported the direct substitution of allylica lcohols with Boc-,Bus-, and Dios-protected amine nucleophiles.…”

“…Theo rganic layer was washed with brine,d ried over MgSO4 and concentrated under vacuum. After cooling, the reaction mixture was poured into water and extracted with EtOAc.…”