1,4‐Dichloro‐ and 1,4‐Dibromo‐2‐butenes as Substrates for Cu‐Catalyzed Asymmetric Allylic Substitution

Copper‐Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Aryl‐ and Alkenylboronates

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Catalytic asymmetric allylic substitution with organometallic reagents is one of the efficient ways of constructing enantioenriched chiral compounds by the formation of a new carbon-carbon bond. Although a significant number of reports have been made on this reaction, particularly using chiral copper complexes as catalysts, [1] the organometallic reagents that can be employed are mostly limited to highly reactive ones, such as Grignard, [2] diorganozinc, [3] and triorganoaluminum reagents. [4] In contrast, the use of milder nucleophiles, such as organoboronic acid derivatives, has been much less explored despite their availability, stability, and ease of handling.

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Copper‐Catalyzed Asymmetric Allylic Alkylation

“…Later on, a similar procedure was applied to commercially available 1,4-dihalo-2-butene substrates 50,51 with impressive complete regiocontrol, [28] imputed to the intramolecular stabilisation of the intermediate copper(III)-allyl complex. Such reactions afforded highly tunable substrates with up to 94 % ee (Scheme 20).…”

Enyne Chlorides: Substrates for Copper‐Catalyzed Asymmetric Allylic Alkylation

“…In the past few years, our group has reported highly regioand enantioselective copper/phosphoramidite catalytic systems for AAA of allylic chlorides with organomagnesium reagents (Scheme 1 a); [3] later, the range of substrates was extended to include b-disubstituted allylic chlorides, 1,4difunctionalized allylic type substrates, etc. [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.…”