Stereodivergent synthesis of α-fluoro α-azaaryl γ-butyrolactones via cooperative copper and iridium catalysis

Tian, Kui; Chang, Xin; Lü, Xiao; Dong, Xiu‐Qin; Wang, Chun‐Jiang

doi:10.1016/j.fmre.2022.07.008

Cited by 16 publications

(2 citation statements)

References 119 publications

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“…In light of the above experimental results and our previous research works, a plausible mechanistic cycle was outlined in Figure to rationalize this protocol. it was initiated by the coordination of [Ir(I)*] and racemic benzoxazinone 1 to generate [Ir(I)*]/( S )- 1 and [Ir(I)*]/( R )- 1 complexes.…”

mentioning

confidence: 63%

Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

Xiang

Zhang

et al. 2023

Org. Lett.

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Chiral benzoxazinones and 4H-3,1-benzoxazines as important motifs are widely found in abundant pharmaceuticals and biological molecules. We herein successfully developed the first kinetic resolution (KR) process of racemic benzoxazinones through Ir-catalyzed asymmetric intramolecular allylation, furnishing a wide range of chiral benzoxazinones and 4H-3,1-benzoxazines with excellent results via outstanding KR performances (with the s factor up to 170). This protocol exhibited broad substrate scope generality and good functional group tolerance, and the chiral 4H-3,1-benzoxazine products could be readily transformed to other useful optically active heterocycles.

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confidence: 63%

Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

Xiang

Zhang

et al. 2023

Org. Lett.

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“…This methodology worked well for a diverse range of azomethine ylides; both aldehyde and ketone derived acyclic imino esters, as well as cyclic keimine esters, showed comparably high reactivity; for the cyclic nucleophiles in particular, synthetic challenging spirocyclic γ-butyrolactone derivatives were constructed in a stereodivergent manner. A mechanistically similar stereodivergent allylation/lactonization of vinylethylene carbonate with α-fluoro α-azaaryl acetates was reported by the same group …”

Section: Dual Metal/metal Catalysismentioning

confidence: 99%

Synergistic Dual Catalysis in Stereodivergent Synthesis

Wei,

Fu,

Wang

et al. 2024

ACS Catal.

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Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, and their relative and absolute configuration often determine their physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only of great significance, but also is highly challenging since the formation of one of the diastereomers is inherently preferred in most asymmetric reactions. Stereodivergent dual catalysis, introduced in 2013 by the Carreira group, perfectly catered to all the requirements for full stereoselectivity control of given reactions since two chiral catalysts are utilized in a synergistic way and act independently, and has now been arguably the most efficient strategy to realize stereodivergent synthesis. This comprehensive review presents an overview of the development of stereodivergent synthesis enabled by synergistic dual catalysis in the past ten years, providing readers with the fundamental attributes as well as the ability, scope, mechanism, as well as limitations of this strategy.

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Pd/Cu Catalyzed Asymmetric Allylation for Stereodivergent Synthesis of Glutamic Acid Derivatives

Li,

Liu,

Han

et al. 2024

Chemistry A European J

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A synergistic Pd/Cu catalyst system has been developed for stereodivergent transformation of Morita‐Baylis‐Hillman (MBH) carbonates and Schiff bases derived from simple amino acids to afford a series of optically active β‐branched γ‐methyleneglutamic acid derivatives with adjacent tertiary/tertiary and quaternary/tertiary stereocenters in high yields (up to 96%) with excellent diastereo‐ and enantioselectivities (>20/1 dr and >99% ee in most cases) under mild conditions. The use of SKP ligand is disclosed to be crucial for the success of the transformation, and in particular allowing the reaction to proceed at low catalyst loading (0.02 mol% for Pd and 0.08 mol% for Cu). The high efficiency of the catalysis was attributed to the formation of intimate ion pair complex A1, composed of Pd‐phosphonium cation and a t‐butoxide anion, which would facilitate the subsequent deprotonation and C‐C coupling events. All four stereoisomers of the β‐branched glutamic acid derivatives were readily prepared by permutation of the catalyst enantiomers. Synthetic utility of the methodology was exemplified by efficient synthesis of a fused pyrrolooxazolidinone with three contiguous chiral centers, highlighting the power of synergistic Pd/Cu catalysis for asymmetric allylic alkylation with MBH carbonates.

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Stereodivergent synthesis of α-fluoro α-azaaryl γ-butyrolactones via cooperative copper and iridium catalysis

Cited by 16 publications

References 119 publications

Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

Synergistic Dual Catalysis in Stereodivergent Synthesis

Pd/Cu Catalyzed Asymmetric Allylation for Stereodivergent Synthesis of Glutamic Acid Derivatives

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