Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

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gem ‐Difluoromethylene Alkyne‐Enabled Diverse C−H Functionalization and Application to the on‐DNA Synthesis of Difluorinated Isocoumarins

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(4), P. 1959 - 1966

Published: Oct. 6, 2020

Using gem-difluoromethylene alkynes as effectors, unprecedented diverse C-H activation/[4+2] annulations of simple benzoic acids are reported. The chemodivergent reaction outcomes well-tuned by Rh/Ir-catalyzed system; in the RhIII catalysis, 3-alkenyl-1H-isochromen-1-one and 3,4-dialkylideneisochroman-1-one skeletons afforded a solvent-dependent manner whereas difluoromethylene-substituted 1H-isochromen-1-ones generated under IrIII -catalyzed system. Mechanistic studies revealed that unusually double β-F eliminations fluorine effect-induced regioselective reductive elimination independently involved to enable distinct modes for divergent product formations. Besides, synthetic application both derivatization obtained diene products on-DNA synthesis DNA-tagged difluorinated isocoumarin have been demonstrated, which manifested great potential utility developed protocols.

Language: Английский

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Access to Multifunctionalized Benzofurans by Aryl Nickelation of Alkynes: Efficient Synthesis of the Anti‐Arrhythmic Drug Amiodarone

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(44), P. 15808 - 15812

Published: Aug. 23, 2019

An unconventional nickel-catalyzed reaction was developed for the synthesis of multifunctionalized benzofurans from alkyne-tethered phenolic esters. The transformation involves generation a nucleophilic vinyl NiII species by regioselective syn-aryl nickelation an alkyne, which then undergoes intramolecular cyclization with phenol ester to yield highly functionalized 1,1-disubstituted alkenes 3-benzofuranyl and (hetero)aryl substituents. methodology can be used late-stage benzofuran incorporation various drug molecules natural products, such as 2-propylvaleric acid, gemfibrozil, biotin, lithocholic acid. Furthermore, this arylative method successfully applied efficient anti-arrhythmic amiodarone.

Language: Английский

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Propargylic Alcohols as Coupling Partners in Transition‐Metal‐Catalyzed Arene C−H Activation

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(23), P. 5238 - 5256

Published: Sept. 21, 2020

Abstract Transition‐metal‐catalyzed site selective arene C−H bond activation concomitant functionalization with various coupling partners gain magnificent attraction in synthetic organic chemistry as complementary to traditional transformations. Mechanistically, these approaches involve directing group assisted concerted metalation‐deprotonation (CMD), migratory insertion, and reductive elimination sequences. In this realm, diverse categories of were employed buddies. Particularly alkynes enormous attention annulating agents. These units coordinates metalcycle through π‐interaction produce annulation outcomes a straightforward manner. Very recently, propargylic alcohols appointed valuable archetypes armoury, they have shown regio‐ chemoselective insertion into primary species via hydroxy chelation. The influential regioselectivity was drawn by dual coordination metal complexes the pendent hydroxyl group. review, we focused on annulations arenes alcohols, which afford intricate cycles well complex acyclic motifs trouble‐free We categorized transformations based number atoms involved along some addition reactions. anticipate pave way towards enhanced endeavours for discovering novel reaction avenues. magnified image

Language: Английский

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Last Decade of Unconventional Methodologies for the Synthesis of Substituted Benzofurans

Molecules, Journal Year: 2020, Volume and Issue: 25(10), P. 2327 - 2327

Published: May 16, 2020

This review describes the progress of last decade on synthesis substituted benzofurans, which are useful scaffolds for numerous natural products and pharmaceuticals. In particular, new intramolecular intermolecular C-C and/or C-O bond-forming processes, with transition-metal catalysis or metal-free summarized. (1) Introduction. (2) Ring generation via cyclization. (2.1) C7a-O bond formation: (route a). (2.2) O-C2 b). (2.3) C2-C3 c). (2.4) C3-C3a d). (3) (3.1) formation a + (3.2) b (3.3) (4) Benzannulation. (5) Conclusion.

Language: Английский

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Construction of 3-Methyl-2-Substituted Benzo[b]furans and 3-Methyl-2-Substituted Benzo[b]thiophenes Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7182 - 7186

Published: May 2, 2024

A concise method for the facile construction of 3-methyl-2-substituted benzo[b]furans and benzo[b]thiophenes using low-cost, abundant, easy-to-use solid calcium carbide instead flammable explosive gaseous acetylene as an original alkyne source, o-bromophenyl ethers or thioethers substrates through intramolecular carbanion-yne cyclization in a 5-exo-dig manner, subsequent double-bond isomerization is described. The simultaneous formation two C–C bonds realized one-step route. wide substrate scope, high yield, simple workup manipulations are also merits this method. synthetic strategy can be suitable gram scale.

Language: Английский

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Dual Directing-Groups-Assisted Redox-Neutral Annulation and Ring Opening of N-Aryloxyacetamides with 1-Alkynylcyclobutanols via Rhodium(III)-Catalyzed C–H/C–C Activations

Organic Letters, Journal Year: 2019, Volume and Issue: 21(8), P. 2823 - 2827

Published: March 27, 2019

A cascade [3 + 2] annulation and ring opening of N-aryloxyacetamides with 1-alkynylcyclobutanols via Rh(III)-catalyzed redox-neutral C–H/C–C activations using internal oxidative O–NHAc −OH as the dual directing groups has been achieved. This reaction provided an efficient regioselective approach to benzofuran derivatives good functional group compatibility high yields.

Language: Английский

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Rhodium(III)-Catalyzed Redox-Neutral Cascade [3 + 2] Annulation of N-Phenoxyacetamides with Propiolates via C–H Functionalization/Isomerization/Lactonization

Organic Letters, Journal Year: 2018, Volume and Issue: 20(22), P. 7131 - 7136

Published: Nov. 8, 2018

A Rh(III)-catalyzed cascade [3 + 2] annulation of N-phenoxyacetamides with propiolates under mild conditions using the internal oxidative O–N bond as directing group has been achieved. This catalytic system provides a regio- and stereoselective access to benzofuran-2(3H)-ones bearing exocyclic enamino motifs exclusive Z configuration selectivity, acceptable good yields functional compatibility. Mechanistic investigations by experimental density theory studies suggest that consecutive process C–H functionalization/isomerization/lactonization is likely be involved in reaction.

Language: Английский

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Recent Synthetic Methodologies for Chalcone Synthesis (2013-2018)

Current Organocatalysis, Journal Year: 2019, Volume and Issue: 6(3), P. 184 - 192

Published: March 11, 2019

An up-to-date short review of the chalcone methodologies is presented, which most interesting and beneficial for choosing desired protocol to synthesize suitable derivatives chalcones. Chalcones are fluorescent, stable compounds contribute synthesis various pharmacologically important heterocyclic structure-based derivatives. Chalcone has displayed a remarkable curative efficiency cure several diseases. Several schemes have been reported employing different catalysts reagents. The development improved α, β-unsaturated carbonyl still on going. In this review, synthetic their recent modification in designing new methods with efficient, economical, eco-friendly high yield discussed.

Language: Английский

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Chiral Allylic Amine Synthesis Enabled by the Enantioselective Cp^XRh(III)-Catalyzed Carboaminations of 1,3-Dienes

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(4), P. 2279 - 2287

Published: Feb. 5, 2021

Considering the importance of chiral allylic amine structural motif and rarity synthetic methods toward their construction, herein, we report a CpXRh(III)-catalyzed enantioselective intermolecular carboamination 1,3-dienes via N-phenoxy amides-derived aryl C–H activation intramolecular amide transfer. The methodology enables direct synthesis variety amines with embedment phenol functionalities proceeds under mild conditions sequential formation completely regioselective C–C bond highly C–N bond. Integrated experimental computational mechanistic studies reveal an unusual Rh(III)–Rh(I)–Rh(III) catalytic pathway, in which alkene insertion/π-allylation/intramolecular nucleophilic substitution cascade was involved for this transformation. Besides, application derivation natural products late-stage assembly bioactive complexes has also been demonstrated, further strengthens utility approach.

Language: Английский

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