An efficient MnCl<sub>2</sub>‐catalyzed tandem acylation‐cross‐coupling reaction of <i>o</i>‐halobenzoyl chloride with diorganyl magnesium compounds

Zhang, Fengmin; Shi, Zhuangzhi; Chen, Feng; Yu, Yuan

doi:10.1002/aoc.1567

Cited by 9 publications

(1 citation statement)

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“…They also play an important role in the organic synthesis due to their high chemoselectivity. In some examples, manganese(II) was employed as the catalyst, such as cross-coupling with ortho-acylated aryl chlorides in good yields. − In this study, manganese(II) chloride (MnCl 2 ), a nontoxic and inexpensive salt, is introduced as a reagent to facilitate the transmetalation of methylation by Grignard that can provide unique reactivity and stereoselectivity under mild reaction conditions (Scheme ). However, MnCl 2 is insoluble in anisole and 2-methyl tetrahydrofuran (2-MeTHF) reaction solvents, which may cause the transmetalation to take place very slowly with Grignard reagent because the kinetics of manganese is unclear.…”

Section: Introductionmentioning

confidence: 99%

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Tong

Zhou

Waldman

2022

Org. Process Res. Dev.

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The introduction of the nontoxic, inexpensive manganese(II) chloride (MnCl 2 ) salt in Grignard methylation to facilitate the transmetalation in reaction solvents of anisole and 2-methyl tetrahydrofuran (2-MeTHF) has provided unique reactivity and stereoselectivity under mild reaction conditions. However, because MnCl 2 is insoluble in anisole and 2-MeTHF, the transmetalation initiation can be slow with the Grignard reagent without adequate milling of MnCl 2 . In addition, the reaction mechanism of manganese involvement and the potential synergies brought by MnCl 2 are unclear. To date, methods to monitor the transmetalation reaction are scarce. The air/moisture sensitivity of this reaction poses significant challenges for standard analytical technologies. In this work, a Raman analyzer with an in situ probe was used to monitor the reaction species, including those arising from the organometallic species in real time and unambiguously. The results demonstrate how Raman spectroscopy is able to elucidate the transmetalation mechanism and detect the formation of the product in real time to follow the reaction successfully.

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Section: Introductionmentioning

confidence: 99%

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Tong

Zhou

Waldman

2022

Org. Process Res. Dev.

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Manganese(II) Chloride

Cahiez

Bélanger

Boudreault

2012

Encyclopedia of Reagents for Organic Synthesis

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Preparation and Reactivity of Organomanganese Compounds

Cahiez

Gager

2010

Patai's Chemistry of Functional Groups

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This chapter deals with the preparation of organomanganese reagents from organolithium or organomagnesium compounds (transmetallation) as well as from organic halides and manganese metal (oxidative addition). The influence of various parameters on the stability of organomanganese reagents is then discussed (nature of the reagent RMnX, R 2 Mn, R 3 MnLI or R 3 MnMgX; effect of ligands and solvents…). The second part of the chapter is devoted to the reactivity of these reagents and to their uses in organic synthesis. They are especially interesting for their chemoselectivity, as illustracted by the addition to aldehydes and ketones, the preparation of ketones by acylation or the copper‐catalyzed conjugate addition to enones, enals and enoates. Organomanganese reagents can also be used to perform various iron, palladium or nickel‐catalyzed cross‐coupling reactions. Manganese salts are efficient catalyst to achieve various homo‐ and heterocoupling reactions using Grignard reagents. They are also used to catalyze the addition of Grignard reagents to acetylenes, 1,3‐dienes and allenes. Finally, various radical cyclization reactions promoted by organomanganates are presented.

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An efficient MnCl₂‐catalyzed tandem acylation‐cross‐coupling reaction of o‐halobenzoyl chloride with diorganyl magnesium compounds

Abstract: An efficient tandem cross-coupling reaction of o-chlorobenzoyl chloride with dialkyl and diaryl magnesium compounds in the presence of manganese (II) chloride was developed, which proceeds in good yield under mild conditions.

Cited by 9 publications

References 42 publications

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Manganese(II) Chloride

Preparation and Reactivity of Organomanganese Compounds

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An efficient MnCl2‐catalyzed tandem acylation‐cross‐coupling reaction of o‐halobenzoyl chloride with diorganyl magnesium compounds

Abstract: An efficient tandem cross-coupling reaction of o-chlorobenzoyl chloride with dialkyl and diaryl magnesium compounds in the presence of manganese (II) chloride was developed, which proceeds in good yield under mild conditions.

Cited by 9 publications

References 42 publications

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Real-Time and In Situ Monitoring of Transmetalation of Grignard with Manganese(II) Chloride by Raman Spectroscopy

Manganese(II) Chloride

Preparation and Reactivity of Organomanganese Compounds

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An efficient MnCl₂‐catalyzed tandem acylation‐cross‐coupling reaction of o‐halobenzoyl chloride with diorganyl magnesium compounds