scholarly journals Fritsch–Buttenberg–Wiechell rearrangement of magnesium alkylidene carbenoids leading to the formation of alkynes

2021 ◽  
Vol 17 ◽  
pp. 1352-1359
Author(s):  
Tsutomu Kimura ◽  
Koto Sekiguchi ◽  
Akane Ando ◽  
Aki Imafuji
Keyword(s):  
Dft Calculations ◽  
Exchange Reaction ◽  
Carbonyl Compounds ◽  
Organometallic Reagents ◽  
Magnesium Exchange

A series of 1-heteroatom-substituted vinyl p-tolyl sulfoxides were prepared and treated with organometallic reagents to evaluate which combination of sulfoxides and organometallic reagents yielded alkynes the most efficiently. The use of 1-chlorovinyl p-tolyl sulfoxide and isopropylmagnesium chloride was optimal for this purpose. A variety of 1-chlorovinyl p-tolyl sulfoxides were prepared from carbonyl compounds and chloromethyl p-tolyl sulfoxide and were converted into alkynes via the sulfoxide/magnesium exchange reaction and subsequent Fritsch–Buttenberg–Wiechell (FBW) rearrangement of the resulting magnesium alkylidene carbenoids. The mechanism of the FBW rearrangement of magnesium alkylidene carbenoids was studied by using 13C-labeled sulfoxides and by using DFT calculations.

Preparation of Functionalized Diorganomagnesium Reagents in Toluene via Bromine or Iodine/Magnesium-Exchange Reactions

Synthesis ◽  
2021 ◽  
Author(s):  
Alexandre Desaintjean ◽  
Fanny Danton ◽  
Paul Knochel
Keyword(s):  
Exchange Reaction ◽  
Nitro Group ◽  
General Formula ◽  
Functional Groups ◽  
Exchange Reactions ◽  
Acyl Chlorides ◽  
Aryl Iodides ◽  
Highly Sensitive ◽  
Wide Range ◽  
Magnesium Exchange

A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents were prepared in toluene within 10 to 120 min between −78 °C and 25 °C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as a triazene or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arenes and alkenes derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.

Direct preparation of polyfunctional amino-substituted arylmagnesium reagents via an iodine–magnesium exchange reaction

2003 ◽  
pp. 396-397 ◽  
Author(s):  
Greta Varchi ◽  
Christiane Kofink ◽  
David M. Lindsay ◽  
Alfredo Ricci ◽  
Paul Knochel
Keyword(s):  
Exchange Reaction ◽  
Direct Preparation ◽  
Magnesium Exchange

Tributylmagnesium ate complex-mediated novel bromine–magnesium exchange reaction for selective monosubstitution of dibromoarenes

2001 ◽  
Vol 42 (29) ◽  
pp. 4841-4844 ◽  
Author(s):  
Takehiko Iida ◽  
Toshihiro Wada ◽  
Koji Tomimoto ◽  
Toshiaki Mase
Keyword(s):  
Exchange Reaction ◽  
Magnesium Exchange

ChemInform Abstract: Selective Halogen-Magnesium Exchange Reaction via Organomagnesium Ate Complex.

ChemInform ◽  
2010 ◽  
Vol 32 (41) ◽  
pp. no-no
Author(s):  
Atsushi Inoue ◽  
Kazuya Kitagawa ◽  
Hiroshi Shinokubo ◽  
Koichiro Oshima
Keyword(s):  
Exchange Reaction ◽  
Magnesium Exchange

New Stereoselective Preparation of (Z)-3-Perfluoroalkyl-3-magnesiated Enoates by an Iodine−Magnesium Exchange Reaction

2004 ◽  
Vol 69 (12) ◽  
pp. 4262-4264 ◽  
Author(s):  
Jérôme Thibonnet ◽  
Alain Duchêne ◽  
Jean-Luc Parrain ◽  
Mohamed Abarbri
Keyword(s):  
Exchange Reaction ◽  
Magnesium Exchange

scholarly journals Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 204
Author(s):  
Hao Xu ◽  
Baochang Man ◽  
Guohua Luo
Keyword(s):  
Dft Calculations ◽  
Exchange Reaction ◽  
Vinyl Chloride ◽  
Density Functional ◽  
Catalytic Mechanism ◽  
Profile Analysis ◽  
Metal Chlorides ◽  
Acetylene Hydrochlorination ◽  
Rate Determining Step ◽  
Activity Sequence

The catalytic mechanism and activation energies of metal chlorides RuCl3, AuCl3, and BaCl2 for 1,2-dichloroethane (DCE)-acetylene exchange reaction were studied with a combination of density functional theory (DFT) calculations and experiments. Two reported reaction pathways were discussed and acetylene-DCE complex pathway was supported through adsorption energy analysis. The formation of the second vinyl chloride monomer (VCM) was proven to be the rate-determining step, according to energy profile analysis. Activity sequence of BaCl2 > RuCl3 > AuCl3 was predicted and experimentally verified. Furthermore, reversed activity sequences of this reaction and commercialized acetylene hydrochlorination reaction were explained: the adsorption abilities of reactants are important for the former reaction, but chlorine transfer is important for the latter.

Recent Advances in the Synthesis of Enantiomerically Enriched Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols through Addition of Organometallic Reagents to Carbonyl Compounds

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1855-1873
Author(s):  
Senthil Narayanaperumal ◽  
Ricardo S. Schwab ◽  
Wystan K. O. Teixeira ◽  
Danilo Yano de Albuquerque
Keyword(s):  
Carbonyl Compounds ◽  
Building Blocks ◽  
Short Review ◽  
Biological Properties ◽  
Enantioselective Synthesis ◽  
Grignard Reagents ◽  
Organometallic Reagents ◽  
Important Family ◽  
Organolithium Reagents ◽  
Organozinc Reagents

Enantiomerically enriched diaryl, aryl heteroaryl, and dihetero­aryl alcohols are an important family of compounds known for their biological properties. Moreover, these molecules are highly privileged scaffolds used as building blocks for the synthesis of pharmaceutically relevant products. This short review provides background on the enantioselective arylation and heteroarylation of carbonyl compounds, as well as, the most significant improvements in this field with special emphasis on the application of organometallic reagents.1 Introduction2 Background on the Enantioselective Synthesis of Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols3 Organozinc Reagents4 Organolithium Reagents5 Grignard Reagents6 Organoaluminum Reagents7 Organotitanium Reagents8 Organobismuth Reagents9 Miscellaneous10 Conclusion

Generation of cycloheptynes and cyclooctynes via a sulfoxide–magnesium exchange reaction of readily synthesized 2-sulfinylcycloalkenyl triflates

2015 ◽  
Vol 51 (42) ◽  
pp. 8745-8748 ◽  
Author(s):  
Suguru Yoshida ◽  
Fumika Karaki ◽  
Keisuke Uchida ◽  
Takamitsu Hosoya
Keyword(s):  
Exchange Reaction ◽  
Magnesium Exchange

Cycloheptynes and cyclooctynes have been efficiently generated via a sulfoxide–magnesium exchange reaction of readily synthesized 2-sulfinylcycloalkenyl triflates.

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