2017
DOI: 10.1021/acs.orglett.7b01022
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Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles

Abstract: A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution of secondary benzyl carbonates with amides and amines proceeds to form the corresponding optically active benzylamines in good yields with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner. Additionally, the asymmetric Pd catalysis can also be applicable to phenol nucleophiles, thus delivering chiral ethers with acceptable yields and enantioselectivity.

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Cited by 24 publications
(4 citation statements)
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“…Benzylic palladium complexes are frequently formed in Pd-catalyzed transformations of benzyl reagents and of styrene derivatives. They can be considered weakly stabilized palladium alkyls by coordination of the aryl ring in a pseudo-allylic (η 3 ) form (Scheme ). Yet, this η 3 interaction, which is made at the expense of the aromaticity of the ring, is easily broken to return to the σ-benzylic form.…”
Section: Introductionmentioning
confidence: 99%
“…Benzylic palladium complexes are frequently formed in Pd-catalyzed transformations of benzyl reagents and of styrene derivatives. They can be considered weakly stabilized palladium alkyls by coordination of the aryl ring in a pseudo-allylic (η 3 ) form (Scheme ). Yet, this η 3 interaction, which is made at the expense of the aromaticity of the ring, is easily broken to return to the σ-benzylic form.…”
Section: Introductionmentioning
confidence: 99%
“…To address these challenges, new synthetic routes have been developed using transition‐metal catalyzed cross‐coupling, reductive coupling, and C−H amination reactions Recently, Doyle reported an elegant Ni‐catalyzed three‐component coupling of benzaldehydes, arylhalides, and N ‐silylamines to afford unsymmetrical benzhydryl amines . In this communication, we describe a new synthetic approach to these important structures that does not require the use of any sensitive reagents or the multistep preparation of the benzhydryl precursors.…”
Section: Methodsmentioning
confidence: 99%
“…Although reductive aminationo fd iarylketones [4] and nucleophilic addition of organometallic reagents to aldimines [5] are potential alternatives, these methods are not effective for secondary amines due to slow formation of iminium intermediates. [6] To address these challenges, new synthetic routesh ave been developed using transition-metal catalyzed cross-coupling, [7,8] reductivec oupling, [9] and CÀHa mination reactions [10] Recently,D oyle reported an elegant Ni-catalyzed three-component coupling of benzaldehydes, arylhalides, and N-silylamines to afford unsymmetrical benzhydryl amines. [11] In this communication, we describe an ew synthetic approacht ot hese im-portant structures that does not require the use of anys ensitive reagents or the multistep preparation of the benzhydryl precursors.…”
mentioning
confidence: 99%
“…However, only a few examples of asymmetric benzylation reactions have been achieved, and the selection of chiral ligands in conjunction with TMs, including palladium and nickel, has made it possible to produce chiral benzylic derivatives (Fig. 1A) (4)(5)(6)(7)(8)(9)(10)(11). In 2010, Trost and co-workers successfully demonstrated a model approach for the asymmetric benzylation of prochiral carbon nucleophiles via palladium catalysis (12)(13)(14).…”
Section: Introductionmentioning
confidence: 99%