Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives

Abstract

Ferrocenylphosphines added to [Pd(µ-Cl)(η 3 -C 3 H 5 )] 2 dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1 -bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial interest.

Palladium(0)-catalyzed amination of allylic natural terpenic functionalized olefins

“…The result obtained with geranyl acetate 5 was less efficient than the one reported by Nguyen et al [18] using palladium-ferrocenylphosphine catalytic systems. it is noteworthy that all amines derived from optically active perillyl acetate 3 exhibit optical activity.…”

“…Recently, Nguyen et al have reported efficient palladium catalytic systems for the allylic amination of monoterpenic acetates [18]. The catalytic systems combining a Pd(ii) precursor and a ferrocenylphosphine ligand shows an excellent selectivity.…”

“…However, although the palladium-catalyzed amination of allylic functionalized simple alkenes has been extensively studied, to our knowledge few works have been devoted to the corresponding reactions using natural terpenic alkenes derivatives [18,26,27]. Previously we have reported that the alkoxycarbonylation and the oxidative cleavage of allylic natural terpenic olefins, offers a very good method respectively for the preparation of new β,γ-unsaturated esters and ketoacids [28,29], which are of considerable value for the perfumery and pharmaceutical industry [30][31][32][33][34], as well as useful synthetic intermediates and chiral building blocks [35][36][37].…”

Myrcene as a Natural Base Chemical in Sustainable Chemistry: A Critical Review

“…Other methods to prepare these amines start on the corresponding acetates and are generated via allylic amination catalyzed by palladium complexes. [157][158][159][160] Because hydroamination occurs with 100 % atom efficiency, meaning all substrate molecules can be found in the product, plenty of investigations to add diethylamine in one step to myrcene have been described (Table 6). 1082 www.chemsuschem.org…”

Novel Palladium‐Catalysed Hydroamination of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems

“…The same amines can be obtained via the allylic amination of the corresponding acetates. [35][36][37][38] Nevertheless, the direct hydroamination of myrcene is proven to be the better route because the acetates are rarely available. If the pathway is telomerisation, the so-called tail-to-tail telomer (tttelomer, 3) is mainly generated.…”