Ruthenium(<scp>ii</scp>)-catalyzed regioselective 1,6-conjugate addition of umpolung aldehydes as carbanion equivalents

Kang, Hyotaik; Li, Chao‐Jun

doi:10.1039/d1sc03732c

Chem. Sci.

2022

DOI: 10.1039/d1sc03732c

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Ruthenium(ii)-catalyzed regioselective 1,6-conjugate addition of umpolung aldehydes as carbanion equivalents

Hyotaik Kang

Chao‐Jun Li

Abstract: Highly regioselective 1,6-conjugate addition was developed using hydrazone as carbanion equivalent catalyzed by ruthenium under mild conditions.

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Cited by 5 publications

(1 citation statement)

References 48 publications

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“…Deprotonation of dithioacetal forms a nucleophilic carbanion which also acts as acyl anionic equivalents . In pathway D, the generation of a carbanionic equivalent occurs by reacting the carbonyl compound with hydrazine to form a hydrazone which then propagates in the reaction to perform conjugate additions . It is worth noting that the hydrazone is activated by metal-catalyzed and stoichiometric bases in the next step.…”

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confidence: 99%

Organobase-Catalyzed Umpolung of Amides: The Generation and Transfer of Carbamoyl Anion

Zhang

Zhu

et al. 2023

J. Org. Chem.

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A novel organobase-catalyzed umpolung reaction of amides was disclosed. This method provides an efficient method to generate and transfer carbamoyl anions. In this transformation, some of the inherent disadvantages of carbamoyl metal were avoided. The mechanistic analysis revealed that the reaction proceeds through polarity inversion of amide, and various carbamoyl anions were applied in the reaction. Moreover, a wide range of substrates was achieved with moderate to excellent yield.

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confidence: 99%

Organobase-Catalyzed Umpolung of Amides: The Generation and Transfer of Carbamoyl Anion

Zhang

Zhu

et al. 2023

J. Org. Chem.

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Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach

Kaur

Singh

2023

J. Org. Chem.

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Brook rearrangement entails the generation of α-oxygenated carbanions via the umpolung process. Recently, these anionic species have been widely utilized for several C−C bond forming strategies, providing various useful frameworks that are difficult to access through conventional approaches. However, the application of this powerful methodology in the development of chiral strategies is still at the nascent stage due to challenges involved in controlling chemoselectivity and enantioselectivity. This synopsis provides a detailed summary of diastereo-and/or enantioselective chemical transformations using [1,2]-phospha-Brook rearrangement.

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Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine

Xia

Cao

Zeng

et al. 2022

JACS Au

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The direct conversion of naturally abundant carbonyl compounds provides a powerful platform for the efficient synthesis of valuable chemicals. In particular, the conversion of ketones to alkenes is a commonly encountered chemical transformation, often achieved via the multistep Shapiro reaction with tosylhydrazone and over stoichiometric organolithium or Grignard reagent. Herein, we report an earth abundant nickel-catalyzed alkenylation of naturally abundant methylene ketones to afford a wide range of alkene derivatives, mediated by hydrazine. The protocol features a broad substrate scope (including alkyl ketones, aryl ketones, and aldehydes), good functional group compatibility, mild reaction conditions, water tolerance, and only environmentally friendly N 2 , H 2 , and H 2 O as theoretical byproducts. Moreover, gram-scale synthesis with good yield and generation of pharmaceutical intermediates highlighted its practical applicability.

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Ruthenium(ii)-catalyzed regioselective 1,6-conjugate addition of umpolung aldehydes as carbanion equivalents

Abstract: Highly regioselective 1,6-conjugate addition was developed using hydrazone as carbanion equivalent catalyzed by ruthenium under mild conditions.

Cited by 5 publications

References 48 publications

Organobase-Catalyzed Umpolung of Amides: The Generation and Transfer of Carbamoyl Anion

Organobase-Catalyzed Umpolung of Amides: The Generation and Transfer of Carbamoyl Anion

Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach

Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine

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