Ruthenium‐Catalyzed C−C Coupling of Terminal Alkynes with Primary Alcohols or Aldehydes: α,β‐Acetylenic Ketones (Ynones) via Oxidative Alkynylation

Ortiz, Eliezer; Evarts, Madeline M.; Strong, Zachary H.; Shezaf, Jonathan Z; Krische, Michael J.

doi:10.1002/anie.202303345

Cited by 7 publications

(4 citation statements)

References 73 publications

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“…Iodide-bound ruthenium catalysts modified by rac -BINAP catalyze the C–C coupling of terminal alkynes with aldehydes (Scheme A) or alcohols (Scheme B) to form α,β-acetylenic ketones . As corroborated by deuterium labeling experiments, oxidative alkynylation occurs through a novel mechanism in which alkyne hydroruthenation delivers a transient vinylruthenium complex that deprotonates the terminal alkyne to form the alkynylruthenium nucleophile.…”

Section: Catalytic Ketone Synthesis From Alcohols or Aldehydesmentioning

confidence: 98%

Intermolecular Metal-Catalyzed C–C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

et al. 2023

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Intermolecular metal-catalyzed C−C couplings of unactivated primary alcohols or aldehydes to form ketones are catalogued. Reactions are classified on the basis of pronucleophile. Protocols involving premetalated reagents or reactants that incorporate directing groups are not covered. These methods represent an emerging alternative to classical multistep protocols for ketone construction that exploit premetalated reagents and/or steps devoted to redox manipulations and carboxylic acid derivatization.

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Section: Catalytic Ketone Synthesis From Alcohols or Aldehydesmentioning

confidence: 98%

Intermolecular Metal-Catalyzed C–C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

et al. 2023

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“…Besides, noteworthy developments have been reported under transition metal catalysis for the synthesis of α-branched ketones from simple ketones via the borrowing hydrogen (BH)/hydrogen atom-transfer (HA) strategy using alcohols as alkylating agents . In recent years, alcohol has been employed as an alkylating source for various C–C and C–N bond-forming reactions through the borrowing hydrogen (BH) − and acceptorless dehydrogenative coupling (ADC) strategies − (Figure a–c). The BH approach is one of the most powerful methodologies utilizing readily available alcohols as an alkylating source and producing green byproducts such as water, thereby avoiding the formation of toxic byproducts.…”

Section: Introductionmentioning

confidence: 99%

Dehydrogenative Coupling of Alcohols with Internal Alkynes under Nickel Catalysis: An Access to β-Deuterated Branched Ketones

Subaramanian,

Gouda,

Roy

et al. 2024

ACS Catal.

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In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C–C and C–N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C–C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of α-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the α-disubstituted ketones to other valuable building blocks, including large-scale synthesis of β-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.

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“…With respect to the metal-catalyzed N -directed oxidative alkynylation of arenes/heteroarenes, the strategy using ruthenium as catalyst still remains unexplored probably due to the formation of alkenylated products . More recently, some works focused on Ru-catalyzed oxidative C–H alkynylation …”

Section: Introductionmentioning

confidence: 99%

Regiodivergent Metal-Catalyzed Oxidative Alkynylation of 2-Arylthiazoles with Terminal Alkynes under Air Conditions

Zhou,

Wang,

Wan

et al. 2024

J. Org. Chem.

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Regiodivergent transition-metal-catalyzed oxidative C5-and ortho-alkynylation of 2-arylthiazoles have been demonstrated. Namely, Pd(II)-catalysis selectively generated C5-alkynylated products from the reaction of 2-arylthiazoles and terminal alkynes. In contrast, Ru(II)-catalysis exclusively provided ortho-alkynylated products from the same substrates. This protocol features a wide substrate scope, good functional group tolerance, high atom-economy, and exclusive regioselectivity. The alkynylated products can be readily converted into highly valuable synthons, which hold potential for applications in the fields of medicinal chemistry and materials science.

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Ruthenium‐Catalyzed C−C Coupling of Terminal Alkynes with Primary Alcohols or Aldehydes: α,β‐Acetylenic Ketones (Ynones) via Oxidative Alkynylation

Cited by 7 publications

References 73 publications

Intermolecular Metal-Catalyzed C–C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

Intermolecular Metal-Catalyzed C–C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents

Dehydrogenative Coupling of Alcohols with Internal Alkynes under Nickel Catalysis: An Access to β-Deuterated Branched Ketones

Regiodivergent Metal-Catalyzed Oxidative Alkynylation of 2-Arylthiazoles with Terminal Alkynes under Air Conditions

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