Identification of a Valuable Kinetic Process in Copper‐Catalyzed Asymmetric Allylic Alkylation

Abstract

Copper bottomed: The application of a previously described process of dynamic kinetic asymmetric transformation to acyclic substrates allowed the identification of a relevant kinetic process in the title reaction (see scheme; CuTC= copper(I) thiophencarboxylate, Naphth= naphthyl). The optimization of the reaction conditions and generality of the method, as well as mechanistic considerations are disclosed

Asymmetric Syntheses of the Flavonoid Diels–Alder Natural Products Sanggenons C and O

“…Further structural complexity was obtained employing enantioselective [4+2] cycloaddition to construct sanggenon C ( 3 ) and sanggenon O ( 4 ) 6 using a unique stereodivergent RRM. 7 …”

Asymmetric Allylic Alkylation of Acyclic Allylic Ethers with Organolithium Reagents

“…[1] The use of metal complexes such as Pd, [2] Mo [3] , or Ir [4] in combination with mainly allylic carbonates or acetates represents an excellent methodology for the use of stabilized nucleophiles in this transformation. On the other hand, Cu-catalyzed asymmetric allylic alkylation (AAA) [5][6][7] is characterized by the formation of CÀC bonds with organometallic reagents. Allylic substrates with good leaving groups, such as allylic halides [6] and allylic phosphates, [7] are typically used in these transformations.…”

“…On the other hand, Cu-catalyzed asymmetric allylic alkylation (AAA) [5][6][7] is characterized by the formation of CÀC bonds with organometallic reagents. Allylic substrates with good leaving groups, such as allylic halides [6] and allylic phosphates, [7] are typically used in these transformations. A major challenge is to accomplish similar catalytic AAA by using allylic substrates with robust protecting groups.…”

Enyne Chlorides: Substrates for Copper‐Catalyzed Asymmetric Allylic Alkylation

“…[4] Additionally, the dynamic kinetic asymmetric transformation process was also studied, and involved using racemic cyclic or acyclic substrates under copper-catalyzed AAA conditions with phosphoramidite ligands. [5] Subsequently, we focused on the use of the more vulnerable and synthetically interesting prochiral substrates, which generate chiral products, 1,4-enynes in this case, as a result of the AAA process (Scheme 1 b)…”

“…[4] Additionally, the dynamic kinetic asymmetric transformation process was also studied, and involved using racemic cyclic or acyclic substrates under copper-catalyzed AAA conditions with phosphoramidite ligands. [5] Subsequently, we focused on the use of the more vulnerable and synthetically interesting prochiral substrates, which generate chiral products, 1,4-enynes in this case, as a result of the AAA process (Scheme 1 b) As far as we know, the AAA on the extended multiple bond system, especially the enyne substrates, has not been studied much. [6] Trost et al have performed an enantioselective molybdenum-catalyzed process on enyne carbonates, with malonate salts as nucleophiles; good regioselectivities were observed in favor of the 1,3-substitution together with excellent ee values (Scheme 2).…”