Enantioselective Formal [4 + 3] Annulations to Access Benzodiazepinones and Benzoxazepinones via NHC/Ir/Urea Catalysis

Li, Yangyang; Li, Shuai; Fan, Tongxiang; Zhang, Zijing; Song, Jin; Gong, Liu‐Zhu

doi:10.1021/acscatal.1c04541

Cited by 24 publications

(11 citation statements)

References 102 publications

(37 reference statements)

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“…A variety of chiral 7-membered heterocycles 28 were successfully constructed in good yields with high enantioselectivities (Scheme 6). 35 The addition of achiral urea OC1 dramatically enhanced the stereocontrol, possibly owing to cooperative catalysis with the chiral NHC. A plausible mechanism is proposed below.…”

Section: π-Allyl-m-type Mcrdsmentioning

confidence: 99%

High-order dipolar annulations with metal-containing reactive dipoles

Zhang

Shi

et al. 2022

Chem. Soc. Rev.

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Section: π-Allyl-m-type Mcrdsmentioning

confidence: 99%

High-order dipolar annulations with metal-containing reactive dipoles

Zhang

Shi

et al. 2022

Chem. Soc. Rev.

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“…N-Heterocyclic carbene (NHC)-mediated umpolung reactivity of aldehydes has enabled numerous highly significant reactions. − In recent years, NHC/transition metal cooperative catalysis has shown its robustness in creating new transformations and hence has received increasing attention. − Within this context, azolium homoenolate/enolate intermediates catalytically generated from NHC and carbonyls can be successfully captured by electrophiles activated by ruthenium, palladium, − iridium, ,, copper, ,− gold, and nickel complexes, leading to synthetically useful transformations and a greater understanding of reaction manifolds possibly occurring with NHC/TM cooperative catalysis. More recently, our group demonstrated that isatin-derived homoenolate equivalent I (Figure A) governs the geometry, facial selectivity, and regioselectivity of the oxindole moiety in a stereodivergent propargylic alkylation reaction .…”

Section: Introductionmentioning

confidence: 99%

Diastereodivergent Desymmetric Annulation to Access Spirooxindoles: Chemical Probes for Mitosis

Wen

Yang

et al. 2023

J. Am. Chem. Soc.

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Spirooxindoles have emerged as promising architectures for engineering biologically active compounds. The diastereodivergent construction of unique scaffolds of this type with full control of continuous chiral centers including an all-carbon quaternary stereogenic center is yet to be developed. Here, we report an unprecedented diastereodivergent desymmetric [3 + 3] annulation of oxabicyclic alkenes with enals enabled by N-heterocyclic carbene (NHC)/Rh cooperative catalysis, leading to a series of enantiomerically enriched spirooxindole lactones with excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to >95:5 dr). The combined catalyst system comprises a rhodium complex that controls the configuration at the electrophilic carbon and an NHC catalyst that controls the configuration at the nucleophilic oxindole-containing carbon; thus, four stereoisomers of the spirooxindole products can be readily obtained simply by switching the configurations of the two chiral catalysts. Transformations of the chiral spirooxindoles delivered synthetically useful compounds. Importantly, those chiral spirooxindoles arrested mammalian cells in mitosis and exhibited potent antiproliferative activities against HeLa cells. Significantly, both absolute and relative configurations exert prominent effects on the bioactivities, underscoring great importance of catalytic asymmetric diastereodivergent synthesis beyond creating useful tools for the exploration of structure−activity relationships.

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“…In comparison with the extensively explored Pd, Ir, or Ni-π-allyl species, as well as Cu-allenylidene species, coupling with chiral NHC-adorned nucleophiles, asymmetric reactions mediated by other types of electrophilic TM-activated intermediates, however, is still comprehensively elusive in this area. Recently, our group ( 50 , 55 – 58 ) demonstrated that the isatin-derived homoenolate equivalent I ( 60 – 63 ) exhibits high facial selectivity and good feasibility with metal-activated electrophiles, providing an important advance to access synthetically valuable oxindole derivatives ( Fig. 1C ).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric redox benzylation of enals enabled by NHC/Ru cooperative catalysis

Wen

Song

et al. 2023

Sci. Adv.

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The development of general methods for asymmetric benzylation of prochiral carbon nucleophiles remains a challenge in organic synthesis. The merging of ruthenium catalysis and N-heterocyclic carbene (NHC) catalysis for asymmetric redox benzylation of enals has been achieved, which opens up strategic opportunities for the asymmetric benzylation reactions. A wide range of 3,3′-disubstituted oxindoles with a stereogenic quaternary carbon center widely existing in natural products and biologically interesting molecules is successfully obtained with excellent enantioselectivities [up to 99% enantiomeric excess (ee)]. The generality of this catalytic strategy was further highlighted by its successful application in the late-stage functionalization of oxindole skeletons. Furthermore, the linear correlation between ee values of NHC precatalyst and the product elucidated the independent catalytic cycle of either the NHC catalyst or the ruthenium complex.

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Enantioselective Formal [4 + 3] Annulations to Access Benzodiazepinones and Benzoxazepinones via NHC/Ir/Urea Catalysis

Cited by 24 publications

References 102 publications

High-order dipolar annulations with metal-containing reactive dipoles

High-order dipolar annulations with metal-containing reactive dipoles

Diastereodivergent Desymmetric Annulation to Access Spirooxindoles: Chemical Probes for Mitosis

Asymmetric redox benzylation of enals enabled by NHC/Ru cooperative catalysis

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