Catalytic enantioselective alkenylation–heteroarylation of olefins: stereoselective syntheses of 5–7 membered azacycles and oxacycles

Ma, Zhaoming; Sun, Lantian; Zhou, Jianrong

doi:10.1039/d2sc07117g

Cited by 10 publications

(5 citation statements)

References 66 publications

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“…9B). Second, we carried out the In reduction of in situ–formed complex ( R,R )-QuinoxP*Co II I 2 in DMF, monitored by ultraviolet-visible (UV-Vis) spectroscopy ( 86 – 88 ) (Fig. 9C, for more details, see the Supplementary Materials).…”

Section: Resultsmentioning

confidence: 99%

Expedient and divergent synthesis of unnatural peptides through cobalt-catalyzed diastereoselective umpolung hydrogenation

Song,

Bai,

et al. 2023

Sci. Adv.

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The development of a reliable method for asymmetric synthesis of unnatural peptides is highly desirable and particularly challenging. In this study, we present a versatile and efficient approach that uses cobalt-catalyzed diastereoselective umpolung hydrogenation to access noncanonical aryl alanine peptides. This protocol demonstrates good tolerance toward various functional groups, amino acid sequences, and peptide lengths. Moreover, the versatility of this reaction is illustrated by its successful application in the late-stage functionalization and formal synthesis of various representative chiral natural products and pharmaceutical scaffolds. This strategy eliminates the need for synthesizing chiral noncanonical aryl alanines before peptide formation, and the hydrogenation reaction does not result in racemization or epimerization. The underlying mechanism was extensively explored through deuterium labeling, control experiments, HRMS identification, and UV-Vis spectroscopy, which supported a reasonable Co I /Co III catalytic cycle. Notably, acetic acid and methanol serve as safe and cost-effective hydrogen sources, while indium powder acts as the terminal electron source.

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Section: Resultsmentioning

confidence: 99%

Expedient and divergent synthesis of unnatural peptides through cobalt-catalyzed diastereoselective umpolung hydrogenation

Song,

Bai,

et al. 2023

Sci. Adv.

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“…al reported a catalytic enantioselective alkenylation‐heterarylation of olefins with good stereoselectivity and broad substrate scope (Scheme 20). [49] The Pd catalyst with Josiphos L1 can be applied to domino couplings of iododialkene 93 with various classes of heteroarenes, including benzothiazole, benzooxazole, thiophene, imidazole, and furan. It was worth noting that C2‐substituted thiophene ( 94 c ) would selectively react at the C5 site near the S atom, and electron‐withdrawing groups show an indispensable role in the activation of imidazole ( 94 d ), thiophene ( 94 e ), and furan ( 94 f ).…”

Section: Reaction With Alkenementioning

confidence: 99%

Transition‐Metal‐Catalyzed Cyclization of Alkenyl Iodide

Jia,

Liu,

Xie

et al. 2023

Adv Synth Catal

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Alkenyl iodide, as an essential precursor and structural unit in organic synthesis, has been widely used in the synthesis of natural products, pharmaceutical pesticides and functional materials. The high reactivity of Csp2‐I bond allowing could lead to form C‐M bond via oxidative addition, and then undergoes C‐M bond transformations to construct new chemical bonds. A variety of valuable scaffolds, in particular the cyclic motifs, could be achieved via designing and synthesis the corresponding alkenyl iodide, which makes this strategy to be a hot topic in synthetic chemistry. In this paper, the recent progress of transition metal‐catalyzed cyclization of alkenyl iodides is summarized, and the possible mechanisms for most transformations are described in detail.

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“…The first challenge pertains to the facile construction of highly congested quaternary all-carbon stereogenic centers, which serve as core motifs in numerous biologically active molecules and natural products . Currently, several elegant synthetic methods, such as Pd-catalyzed relay Heck reactions, allylic substitution, and enantioconvergent cross-coupling of tertiary alkyl electrophiles, are capable of achieving this formidable task. − The second and more challenging obstacle involves the construction of vicinal stereogenic centers, necessitating precise control of both diastereoselectivity and enantioselectivity . Noteworthy contributions have been made by Fu group, who seminally developed nickel-catalyzed doubly enantioconvergent Negishi couplings for the construction of contiguous tertiary-tertiary stereocenters .…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Huang,

Xi,

Pan

et al. 2024

J. Am. Chem. Soc.

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The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as a straightforward and efficient tool for stereoselectively forging C−C bond. Nevertheless, the creation of acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within the domain of cross-coupling chemistry despite their prominence in various bioactive small molecules. Herein, we describe a palladium-catalyzed asymmetric multicomponent cross-coupling of trisubstituted alkene with aryl diazonium salts and arylboronic acids to realize the formation of tertiary-quaternary carbon centers with high regio-, distereo-, and enantioselectivity. Specifically, the precise manipulation of the stereoconfiguration of trisubstituted alkenes enables the divergent stereoselective cross-coupling reaction, thus allowing for the facile construction of all four enantiomers. Harnessing the ligand-swap strategy involving a chiral bisoxazoline and an achiral fumarate individually accelerates the enantioselective migratory insertion and reductive elimination step in the cross-coupling process, as supported by density functional theory (DFT) calculations, thus obviating the requirement for a neighboring directing group within the internal olefin skeleton.

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Catalytic enantioselective alkenylation–heteroarylation of olefins: stereoselective syntheses of 5–7 membered azacycles and oxacycles

Abstract: Catalytic enantioselective domino alkenylation-heteroarylation of nonconjugated iododienes proceeded with excellent stereoselectivity and broad scopes of substrates. The reaction enables stereoselective syntheses of substituted azacycles and oxacycles such as piperidine, pyrrolidine,...

Cited by 10 publications

References 66 publications

Expedient and divergent synthesis of unnatural peptides through cobalt-catalyzed diastereoselective umpolung hydrogenation

Expedient and divergent synthesis of unnatural peptides through cobalt-catalyzed diastereoselective umpolung hydrogenation

Transition‐Metal‐Catalyzed Cyclization of Alkenyl Iodide

Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

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