Chelation-Based Homologation by Reaction of Organometallic Reagents with O-Alkyl S-Pyridin-2-yl Thiocarbonates: Synthesis of Esters from Grignard Reagents

Usami, Shun; Suzuki, Takeshi; Mano, Koudai; Tanaka, Kosaku; Hashimoto, Yoshimitsu; Morita, Nobuyoshi; Tamura, Osamu

doi:10.1055/s-0037-1611868

Synlett

2019

DOI: 10.1055/s-0037-1611868

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Chelation-Based Homologation by Reaction of Organometallic Reagents with O-Alkyl S-Pyridin-2-yl Thiocarbonates: Synthesis of Esters from Grignard Reagents

Shun Usami¹,

Takeshi Suzuki²,

Koudai Mano³

et al.

Abstract: The one-carbon homologative esterification of Grignard reagents with O-alkyl S-pyridin-2-yl thiocarbonates has been explored. This one-step synthesis of esters from Grignard reagents is the first case to involve chelation-stabilized intermediates.

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Cited by 3 publications

References 7 publications

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Direct C−H Sulfuration: Synthesis of Disulfides, Dithiocarbamates, Xanthates, Thiocarbamates and Thiocarbonates

Sun,

Xu,

Yang

et al. 2024

Chemistry An Asian Journal

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In light of the important biological activities and widespread applications of organic disulfides, dithiocarbamates, xanthates, thiocarbamates and thiocarbonates, the continual persuit of efficient methods for their synthesis remains crucial. Traditionally, the preparation of such compounds heavily relied on intricate multi‐step syntheses and the use of highly prefunctionalized starting materials. Over the past two decades, the direct sulfuration of C–H bonds has evolved into a straightforward, atom‐ and step‐economical method for the preparation of organosulfur compounds. This review aims to provide an up‐to‐date discussion on direct C–H disulfuration, dithiocarbamation, xanthylation, thiocarbamation and thiocarbonation, with a special focus on describing scopes and mechanistic aspects. Moreover, the synthetic limitations and applications of some of these methodologies, along with the key unsolved challenges to be addressed in the future are also discussed. The majority of examples covered in this review are accomplished via metal‐free, photochemical or electrochemical approaches, which are in alignment with the overraching objectives of green and sustainable chemistry. This comprehensive review aims to consolidate recent advancements, providing valuable insights into the dynamic landscape of efficient and sustainable synthetic strategies for these crucial classes of organosulfur compounds.

show abstract

Direct C−H Sulfuration: Synthesis of Disulfides, Dithiocarbamates, Xanthates, Thiocarbamates and Thiocarbonates

Sun,

Xu,

Yang

et al. 2024

Chemistry An Asian Journal

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show abstract

Synthesis and Versatile Utilization of 2‐Pyridyl and Pyrimidyl‐Related Reagents

Lee

2020

Bulletin Korean Chem Soc

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Active (thio)esters and amides were prepared from carboxylic acids and several reagents containing 2‐pyridyl or pyrimidyl moiety. Active (thio)carbonates, thionocarbonate, and thiourea were prepared from (thio)phosgene and 2‐hydroxypyridine or 2‐mercaptopyridine. The acylation of active (thio)esters and amides containing 2‐pyridyl or pyrimidyl groups with various organometallics afforded ketones, aldehydes, esters, amides, and β‐keto esters. The alkoxycarbonylation of active (thio)carbonates with Grignard reagents and amines afforded esters and carbamates, respectively. Active di(thiono)carbonates and thiourea containing the 2‐pyridyl or pyrimidyl moiety have been used in the dehydration of carboxylic acids/alcohols or aldoximes, dehydrosulfurization of thioureas, and (thio)carbonyl transfer of diols or amines to produce esters or nitriles, carbodiimides, cyclic carbonates or isothiocyanates, respectively.

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O-Alkyl S-(Pyridin-2-yl)carbonothiolates: Operationally Simple and Highly Nitrogen-Selective Reagents for Alkoxy Carbonylation of Amino Groups

Suzuki¹,

Tanaka²,

Hashimoto³

et al. 2020

Synlett

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Chelation-Based Homologation by Reaction of Organometallic Reagents with O-Alkyl S-Pyridin-2-yl Thiocarbonates: Synthesis of Esters from Grignard Reagents

Abstract: The one-carbon homologative esterification of Grignard reagents with O-alkyl S-pyridin-2-yl thiocarbonates has been explored. This one-step synthesis of esters from Grignard reagents is the first case to involve chelation-stabilized intermediates.

Cited by 3 publications

References 7 publications

Direct C−H Sulfuration: Synthesis of Disulfides, Dithiocarbamates, Xanthates, Thiocarbamates and Thiocarbonates

Direct C−H Sulfuration: Synthesis of Disulfides, Dithiocarbamates, Xanthates, Thiocarbamates and Thiocarbonates

Synthesis and Versatile Utilization of 2‐Pyridyl and Pyrimidyl‐Related Reagents

O-Alkyl S-(Pyridin-2-yl)carbonothiolates: Operationally Simple and Highly Nitrogen-Selective Reagents for Alkoxy Carbonylation of Amino Groups

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