Catalytic Enantioselective Synthesis of Bicyclic Lactam <i>N</i>,<i>S</i>‐Acetals in One Pot by Cascade Transformations

Zhang, Kaiheng; Deiana, Luca; Grape, Erik Svensson; Inge, A. Ken; Córdova, Armando

doi:10.1002/ejoc.201900923

Eur J Org Chem

2019

DOI: 10.1002/ejoc.201900923

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Catalytic Enantioselective Synthesis of Bicyclic Lactam N,S‐Acetals in One Pot by Cascade Transformations

Kaiheng Zhang

Luca Deiana

Erik Svensson Grape

et al.

Abstract: A versatile strategy for the enantioselective synthesis of bicyclic lactam N,S‐acetals by one‐pot cascade transformations is disclosed. The transformation of readily available substrates is promoted by chiral amines and creates bicyclic or tricyclic lactam N,S‐acetals with high chemo‐ and stereoselectivity (up to > 99.5:0.5 dr and > 99 % ee) in one‐pot operations.

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Cited by 3 publications

(1 citation statement)

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“…Additionally chiral N , N ′-aminals have been reported to also be used in peptide mimetic studies, within the so-called retro-inverso peptides . After our initial work with nitrogen additions to imines, numerous examples of carbon, oxygen, and sulfur nucleophiles were also subsequently described. However, lingering questions about the exact catalyst in many of these asymmetric additions have persisted since the studies by Ishihara et al and List et al on the nature of the true catalyst for some CPA mediated reactions.…”

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confidence: 86%

Imine Amidation Catalyzed by a Chiral VAPOL Calcium Phosphate

Cao

Antilla

2020

Org. Lett.

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Over the last 16 years, chiral phosphoric acids (CPAs) have been shown to be excellent asymmetric catalysts, very effectively used in constructing chiral molecules with high enantiocontrol. In 2010, Ishihara et al. discovered that chiral metal phosphate complexes (or salts) could be found in substantial quantities, as contaminates, in some reported CPA-catalyzed reactions (Angew. Chem., Int. Ed.20104938233826). These metal phosphates were shown to actually catalyze the reactions in addition to CPAs. In this work, we have investigated in depth a reaction first reported to be catalyzed by CPAs based on a vaulted bis-phenanthrol (VAPOL) backbone. We have found that VAPOL metal phosphates were, in fact, superior catalysts for this reaction. Upon optimization, a wide substrate scope, low catalyst loading, and mild conditions could provide intermolecular imine amidation reactions producing chiral N,N′-aminal products in high yields and with excellent ee values (up to >99% yield, >99% ee).

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confidence: 86%

Imine Amidation Catalyzed by a Chiral VAPOL Calcium Phosphate

Cao

Antilla

2020

Org. Lett.

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Solvent Dependency in Stereoselective δ‐Lactam Formation of Chiral α‐Fluoromalonate Derivatives: Stereodivergent Synthesis of Heterocycles with Fluorine Containing Stereocenters Adjacent to Tertiary Stereocenters

et al. 2022

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The discovery and investigation of solvent dependency in stereoselective intramolecular amidation of chiral 5-aminofunctionalized-2-fluoromalonate ester derivatives, which gives access to highly functionalized δ-lactams with a quaternary fluorine-containing stereocenter, is disclosed. Experimental work together with density functional theory calculations led to understanding of how to direct and switch the stereochemical outcome of the stereoselective δ-lactam formation. The merging of this solvent-dependent stereoselective switch with asymmetric catalysis and cascade reactions gives access to an unprecedented strategy for stereodivergent synthesis of all possible stereoisomers of fluorine-containing stereocenters adjacent to tertiary stereocenters of a wide range of heterocyclic compounds with 95-> 99% ee in one-pot. It is also useful for application in total synthesis of fluorine-containing pharmaceuticals.

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Enantioselective synthesis of chiral α-alkynylated thiazolidones by tandemS-addition/acetalization of alkynyl imines

Wang

Liu

et al. 2020

Org. Biomol. Chem.

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Catalytic Enantioselective Synthesis of Bicyclic Lactam N,S‐Acetals in One Pot by Cascade Transformations

Cited by 3 publications

References 65 publications

Imine Amidation Catalyzed by a Chiral VAPOL Calcium Phosphate

Imine Amidation Catalyzed by a Chiral VAPOL Calcium Phosphate

Solvent Dependency in Stereoselective δ‐Lactam Formation of Chiral α‐Fluoromalonate Derivatives: Stereodivergent Synthesis of Heterocycles with Fluorine Containing Stereocenters Adjacent to Tertiary Stereocenters

Enantioselective synthesis of chiral α-alkynylated thiazolidones by tandemS-addition/acetalization of alkynyl imines

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