Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one

Xu, Youlong; Wang, Hongkai; Yang, Zhuang; Zhou, Yuqiao; Liu, Yangbin; Feng, Xiaoming

doi:10.1016/j.chempr.2022.04.006

Cited by 72 publications

(13 citation statements)

References 90 publications

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“…Recently, Feng and co‐workers reported a stereodivergent synthesis of rocaglaol, which possesses anticancer activity, by Ir/Ni‐ and Ir/Co‐catalyzed asymmetric allylic substitution (Scheme 15). [35] The N , N ′‐dioxide complexes were used as Lewis acids to activate the substituted benzofuran‐3(2 H )‐one 28 . By using Ir/Ni or Ir/Co bimetallic catalysis, all four stereoisomers of the product were furnished under mild reaction conditions in excellent yields and with good stereoselectivities.…”

Section: Stereodivergent Allylic Substitutionmentioning

confidence: 99%

Bimetallic Catalysis in Stereodivergent Synthesis

et al. 2022

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Bimetallic catalysis has emerged as an efficient strategy for the development of new chemical reactions. Importantly, this strategy also provides a simple and powerful platform for stereodivergent synthesis, whereby all the possible stereoisomers of products bearing two stereocenters can be easily prepared from the same set of starting materials. In this Minireview, the development of stereodivergent allylic substitution, propargylic substitution, hydrofunctionalization, and annulation based on bimetallic catalysis has been summarized. It is expected that more bimetallic catalytic systems will be developed and applied for the stereodivergent synthesis of valuable molecules.

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Section: Stereodivergent Allylic Substitutionmentioning

confidence: 99%

Bimetallic Catalysis in Stereodivergent Synthesis

et al. 2022

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“…Asymmetric Ir(I)-catalyzed allylic alkylation reactions have attracted significant attention in recent years due to their high regio- and enantioselectivity and are a most versatile and powerful method to construct C–C and C-heteroatom bonds. − Generally, amine or enolate formed by deprotonation of carbonyl precursors has been used as nucleophiles to produce chiral, branched products (Scheme a). − Application of prochiral nucleophiles in these reactions would produce vicinal chiral stereocenters, but the stereochemical control of reactions with a single Ir(I) catalyst is difficult. The introduction of a second catalyst with the aim of catalyzing the generation of a chiral nucleophile which could participate this Ir(I)-catalyzed substitution is an effective but challenging solution. − Carreira and co-workers developed the first dual enamine catalysis and Ir(I)-catalyzed allylic substitution to provide a stereodivergent access to four stereoisomers (Scheme b) . Recently, Zhang, Hartwig, Wang, and others developed synergistic asymmetric bimetallic Cu/Ir-catalyzed allylic alkylation of azomethine ylides and azaaryl acetamides. − These reactions can be used for the stereodivergent construction of vicinal tertiary and tetrasubstituted carbon stereocenters (Scheme c).…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Dual Cu/Ir Catalysis: Stereodivergent Synthesis of Chiral β-Lactams with Adjacent Tertiary/Quaternary/Tertiary Stereocenters

Song

Yang

et al. 2023

ACS Catal.

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A stereodivergent synthesis of chiral β-lactams with contiguous tertiary/quaternary/tertiary stereocenters has been achieved by a Cu/Ir-catalyzed three-component interrupted Kinugasa allylic alkylation reaction. The two catalysts independently exert high local stereocontrol, providing access to four of the eight possible stereoisomers in high yields with >99% ee. The features of this strategy are the asymmetric simultaneous dual metal-catalyzed cascade reactions with stereoselective coupling of highly transient organometallic intermediates.

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“…Herein, we attempted to construct both the stereogenic centers using a binary catalytic system, as shown in Fig. 1c 18 – 35 . The product possessed many transformative functionalities with two chiral centers in a small molecule.…”

Section: Introductionmentioning

confidence: 99%

Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst

Tanaka

Yoshimura

et al. 2022

Nat Commun

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Abstractα-Alkylation of a β-keto ester is a frequently used reaction for carbon–carbon bond formation. However, extension to a stereoselective reaction remains a significant challenge, because the product easily racemizes under acidic or basic conditions. Here, we report a hybrid system consisting of Pd and Ru complexes that catalyzes the asymmetric dehydrative condensation between cinnamyl-type allylic alcohols and β-keto esters. α-Non-substituted β-keto ester can be allylated to afford an α-mono-substituted product with high regio-, diastereo-, and enantioselectivity. No epimerization occurs owing to the nearly neutral conditions, which is achieved by a rapid proton transfer from Pd-enolate formation to Ru π-allyl complex formation. Four diastereomers can be synthesized on demand by changing the stereochemistry of the Pd or Ru complex. Eight stereoisomers with three adjacent stereogenic centers can be synthesized by employing diastereoselective reduction of the ketone in the products. The formal synthesis of (+)-pancratistatin demonstrates the utility of the reaction.

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Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one

Cited by 72 publications

References 90 publications

Bimetallic Catalysis in Stereodivergent Synthesis

Bimetallic Catalysis in Stereodivergent Synthesis

Simultaneous Dual Cu/Ir Catalysis: Stereodivergent Synthesis of Chiral β-Lactams with Adjacent Tertiary/Quaternary/Tertiary Stereocenters

Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst

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