Nickel‐Catalyzed Asymmetric Reductive Carbo‐Carboxylation of Alkenes with CO₂

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14068 - 14075

Published: April 1, 2021

Abstract Reductive carboxylation of organo (pseudo)halides with CO 2 is a powerful method to provide carboxylic acids quickly. Notably, the catalytic reductive carbo‐carboxylation unsaturated hydrocarbons via fixation highly challenging but desirable approach for structurally diverse acids. There are only few reports and no examples alkenes transition metal catalysis. We report first asymmetric nickel A variety aryl (pseudo)halides, such as bromides, triflates inert chlorides particular note, undergo reaction smoothly give important oxindole‐3‐acetic acid derivatives bearing C3‐quaternary stereocenter. This transformation features mild conditions, wide substrate scope, facile scalability, good excellent chemo‐, regio‐ enantioselectivities. The highlights formal synthesis (−)‐Esermethole, (−)‐Physostigmine (−)‐Physovenine, total (−)‐Debromoflustramide B, (−)‐Debromoflustramine B (+)‐Coixspirolactam A; thereby, opening an avenue chiral natural products .

Language: Английский

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Electrooxidative palladium- and enantioselective rhodium-catalyzed [3 + 2] spiroannulations

Chemical Science, Journal Year: 2022, Volume and Issue: 13(9), P. 2783 - 2788

Published: Jan. 1, 2022

Despite indisputable progress in the development of electrochemical transformations, electrocatalytic annulations for synthesis biologically relevant three-dimensional spirocyclic compounds has as yet not been accomplished. In sharp contrast, herein, we describe palladaelectro-catalyzed C-H activation/[3 + 2] spiroannulation alkynes by 1-aryl-2-naphthols. Likewise, a cationic rhodium(iii) catalyst was shown to enable electrooxidative [3 spiroannulations via formal C(sp3)-H activations. The versatile featured broad substrate scope, employing electricity green oxidant lieu stoichiometric chemical oxidants under mild conditions. An array enones and diverse spiropyrazolones, bearing all-carbon quaternary stereogenic centers were thereby accessed user-friendly undivided cell setup, with molecular hydrogen sole byproduct.

Language: Английский

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Switching between the [2π+2σ] and Hetero‐[4π+2σ] Cycloaddition Reactivity of Bicyclobutanes with Lewis Acid Catalysts Enables the Synthesis of Spirocycles and Bridged Heterocycles

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 11, 2024

Abstract The exploration of the complex chemical diversity bicyclo[n.1.1]alkanes and their use as benzene bioisosteres has garnered significant attention over past two decades. Regiodivergent syntheses thiabicyclo[4.1.1]octanes (S‐BCOs) highly substituted bicyclo[2.1.1]hexanes (BCHs) using a Lewis acid‐catalyzed formal cycloaddition bicyclobutanes (BCBs) 3‐benzylideneindoline‐2‐thione derivatives have been established. first hetero‐(4+3) BCBs, catalyzed by Zn(OTf) 2 , was achieved with broad substrate scope under mild conditions. In contrast, less electrophilic BCB ester undergoes Sc(OTf) 3 ‐catalyzed [2π+2σ] reaction 1,1,2‐trisubstituted alkenes, yielding BCHs spirocyclic quaternary carbon center. Control experiments preliminary theoretical calculations suggest that diastereoselective product formation may involve concerted between zwitterionic intermediate E ‐1,1,2‐trisubstituted alkenes. Additionally, nucleophilic ring‐opening mechanism.

Language: Английский

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C–H activation-initiated spiroannulation reactions and their applications in the synthesis of spirocyclic compounds

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(12), P. 2324 - 2338

Published: Jan. 1, 2024

This review summarizes the most recent progress made in C–H bond activation-initiated spiroannulation reactions and their applications construction of structurally diverse biologically valuable spirocyclic scaffolds.

Language: Английский

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Expeditious entry into carbocyclic and heterocyclic spirooxindoles

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(29), P. 5651 - 5693

Published: Jan. 1, 2022

Recent advances in the chemistry of base-, metal-, nano-metal and organo-catalyst mediated achiral chiral versions structurally diverse pharmaceutically relevant spirooxindoles are gently reviewed.

Language: Английский

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Highly Stereodivergent Synthesis of Chiral C4-Ester-Quaternary Pyrrolidines: A Strategy for the Total Synthesis of Spirotryprostatin A

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3391 - 3396

Published: May 10, 2023

In this work, we disclose two sets of highly diastereo- and enantioselective [3 + 2] cycloadditions iminoesters with various α-substituted acrylates, especially for sterically hindered weakly activated α-aryl or alkyl-substituted acrylates alkenal, alkynal, unstable aliphatic aldehyde-derived iminoesters, catalyzed by the AgHMDS/DTBM-Segphos Ag2O/CA-AA-Amidphos catalytic system, achieving stereodivergent synthesis chiral C4-ester-quaternary exo- endo-pyrrolidines high yields excellent enantioselectivities (up to >99:1 dr >99% ee). More importantly, gram-scale synthetic exo-adduct displays significant applications in aspect realizing total spirotryprostatin A alkaloid via nine steps a 36% overall yield.

Language: Английский

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Advances in Catalytic Asymmetric Reactions Involving o-Hydroxybenzyl Alcohols

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(3), P. 974 - 974

Published: Jan. 1, 2023

a 江苏师范大学化学与材料科学学院 江苏徐州 221116

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Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1294 - 1304

Published: Jan. 7, 2025

Given the widespread presence of spirocyclic scaffolds in natural products and pharmacologically relevant synthetic compounds, development efficient methodologies for their construction holds great importance medicinal chemistry pharmaceutical research. In this study, a general photochemical dearomative spirocyclization nonactivated arenes has been established. The key to method lies ability amine-borane radicals activate aryl bromides iodides via halogen-atom transfer, thereby allowing conversion halides into corresponding subsequent chemodivergent transformations. remarkable compatibility versatility 1,4-difunctionalization is showed by rapid assembly structurally diverse 1,4-cyclohexadiene-based spirocycles incorporating oxindole, indoline, or dihydrobenzofuran subunits. Moreover, potential utility protocol exemplified formal total synthesis vasopressin V2 receptor antagonist Satavaptan.

Language: Английский

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CO₂^•– Enabled Synthesis of Phenanthridinones, Oxindoles, Isoindolinones, and Spirolactams

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

We report herein that photoinduced CO2•– enabled reductive intramolecular radical cyclization of a variety aryl iodide derivatives to the corresponding phenanthridinone, oxindole, isoindolinone, and spirolactam in good yields. Preliminary mechanistic studies suggested generation through homolysis cesium formate presence light, further involvement was directly proved by trapping with diphenyl styrene TEMPO.

Language: Английский

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Asymmetric Synthesis of Strained Multichiral Spirocyclobutanes through Cage-Confined Cross [2 + 2] Photocycloaddition

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 14, 2025

Chiral spirocycles possess the ability to undergo diverse modifications in three-dimensional space, offering advantages terms of physicochemical property and structural variability over conventional organic scaffolds holding promising potential for design biologically active molecules drugs. Among them, highly strained spirocyclobutanes with multiple chiral center-containing four-membered rings have attracted significant attention, but their viable efficient synthesis poses a great challenge. By virtue cage-confined asymmetric photocatalysis, we successfully construct spirocycle bispirocycle compounds containing quaternary tertiary carbon centers cyclobutane through cross [2 + 2] photocycloaddition visible-light-induced mild reactions. The mechanistic studies unveil that open pockets cage photoreactor facilitate dynamic bimolecular recognition render preferential heteromolecular cross-cycloaddition enhanced reactivity, unconventional enantioselectivity, good substrate tolerance, providing direction enzyme-mimetic catalyst challenging photochemical transformations.

Language: Английский

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