Activation of Allyl Alcohols as Allyl Cations, Allyl Anions, and Amphiphilic Allylic Species by Palladium

Abstract

Palladium/Et 3 B induces allyl alcohols to undergo electrophilic allylation of soft carbonucleophiles (pK a 5-14), alkyl aldehydes at the α-position, and amines, indoles, and tryptophan at the 3-position. The same catalyst, and also Pd/Et 2 Zn, also effect the generation of allyl anions from allyl alcohols, which react with aromatic and aliphatic aldehydes and imines to furnish homoallyl alcohols and homoallylamines, respectively, in good yields. 2-Methylenepropane-1,3-diol

Synthesis of Substituted Indenes through Iron‐Catalyzed Annulation of Benzylic Alcohols with Alkynes

“…Recently, much attention has been directed towards Lewis acid-catalyzed direct hydroxy substitution of benzylic, allylic and propargylic alcohols with a variety of nucleophiles as a powerful method for the construction of carbon-carbon and carbon-heteroatom bonds. [2][3][4][5] Despite significant advances in this area, few existing methods allow for the construction of the ring nucleus. [6,7] And all the previously reported annulations are limited to functionalized benzylic alcohols.…”

Palladacycle‐Catalyzed Tandem Allylic Amination/Allylation Protocol for One‐Pot Synthesis of 2‐Allylanilines from Allylic Alcohols

“…[1,2] However, due to the inertness of the hydroxy moiety in such scenarios, direct substitutions of allylic alcohols typically require high temperatures, [3] neat conditions, [4] or considerable amounts of activators. [5][6][7][8][9][10][11][12][13][14] To date, there are several reports on the transition metal-catalyzed allylic amination of allylic alcohols or allylic alcohol derivatives with arylamines leading to the predominant generation of N-allylanilines via C À N bond formation.…”

Cationic Bismuth-Catalyzed Hydroamination and Direct Substitution of the Hydroxy Group in Alcohols with Amides

“…Alcohols are usually transformed into the corresponding halides, carboxylates, carbonates, phosphonates, or related compounds with good leaving ability. The process inevitably produces A number of transition-metal-catalyzed direct allylic aminations have been reported [23][24][25]. However, efficient catalysts that promote the direct allylic aminations without any stoichiometric activators under mild reaction conditions are rather limited [26][27][28][29][30][31][32].…”