Use of Menthyl 2-Methoxynaphthalene-1-sulfinates in the Andersen Synthesis of Optically Active Sulfoxides. Facile Cleavage by Grignard Reagents of Some Aromatic Methyl Ethers

1994 ◽  
Vol 47 (10) ◽  
pp. 1925 ◽  
Author(s):  
KH Bell ◽  
LF Mccaffery
Keyword(s):  
Grignard Reagent ◽  
Methoxy Group ◽  
Optically Active ◽  
Grignard Reagents ◽  
Sulfinyl Group

The pure crystalline diastereomers (1R,2S,5R)-menthyl (R)- and (S)-2-methoxynaphthalene-1-sulfinate (1b) have been prepared and, by reaction with Grignard reagents (the Andersen procedure), converted into optically active alkyl and aryl 2-methoxynaphthyl sulfoxides in 67-77% yields. Use of an excess of Grignard reagent results in facile O-alkyl cleavage of the methoxy group to the corresponding naphthol or a competing loss of the alkyl- or aryl- sulfinyl group to form 2-methoxynaphthalene. Pure diastereomers of menthyl 2,7- dimethoxynaphthalene-1-sulfinate (2b) and menthyl 4-methoxynaphthalene-1-sulfinate (3b) have also been prepared and their reactions with Grignard reagents have been studied.

THE REDUCTION, ENOLATE FORMATION, AND SOLVOLYSIS OF GRIGNARD REAGENTS IN OPTICALLY ACTIVE MEDIA

1957 ◽  
Vol 35 (8) ◽  
pp. 900-910 ◽  
Author(s):  
Norman Allentoff ◽  
George F Wright
Keyword(s):  
Grignard Reagent ◽  
Optically Active ◽  
Grignard Reagents ◽  
Inactive State ◽  
Active Media

The sec-butylbenzene produced by solvolysis of 2-phenyl-2-chlorobutane Grignard reagent in (+) 2,3-dimethoxybutane and benzene is optically inactive. The 2-↓-isopropyl-4-↑-methylcyclohexanols obtained by the reducing action of isopropyl Grignard reagent on racemic 2-↓-isopropyl-4-↑-methylcyclohexanone in (+) dimethoxybutane are optically active to the extent of 6 and 15%. The bromomagnesium enolates obtained by the action of isopropyl Grignard reagent on racemic 2-↓-isopropyl-4-↑-methylcyclohexanone in (+) dimethoxybutane regenerate the parent ketone in an optically inactive state but the diastereomeric 2-↑-isopropyl-4-↑-methylcyclohexanone also produced is optically active to the extent of about 6%.

THE SIGNIFICANCE OF HALIDE IN GRIGNARD REAGENTS

1964 ◽  
Vol 42 (11) ◽  
pp. 2474-2479 ◽  
Author(s):  
Warren French ◽  
George F Wright
Keyword(s):  
Optical Activity ◽  
Magnesium Chloride ◽  
Grignard Reagent ◽  
Methyl Chloride ◽  
Optically Active ◽  
Grignard Reagents ◽  
The Difference

The optical activity of 1-phenylethanol from benzaldehyde and methyl chloride Grignard reagent coordinated with (+)2,3-dimethoxybutane is about one fourth of that found for the same product when bis-methylmagnesium is the reagent. The difference has been attributed to the relative coordinating power of magnesium chloride versus the optically active ether.

The addition of organometallic reagents to tetramesityldigermene

2002 ◽  
Vol 80 (11) ◽  
pp. 1387-1392 ◽  
Author(s):  
Kyle L Fujdala ◽  
David W.K Gracey ◽  
Erica F Wong ◽  
Kim M Baines
Keyword(s):  
Ligand Exchange ◽  
Grignard Reagent ◽  
Thermal Conditions ◽  
Grignard Reagents ◽  
Ethylmagnesium Bromide ◽  
Organometallic Reagent ◽  
Organometallic Reagents ◽  
Thermal Cleavage

The thermolysis and photolysis of hexamesitylcyclotrigermane in the presence of ethylmagnesium bromide has been investigated. Under photochemical conditions, ethyldimesitylgermane, 1,2-diethyl-1,1,2-trimesityldigermane and ethyl-1,1,2,2-tetramesityldigermane were isolated and, under thermal conditions, 1,2,2-triethyl-1,1-dimesityl digermane and 2,2-diethyl-1,1,1-trimesityldigermane were isolated. The photolysis of hexamesitylcyclotrigermane in the presence of methyllithium has also been investigated. In both cases, the organometallic reagent adds to tetramesityl digermene and dimesitylgermylene formed by photochemical or thermal cleavage of the cyclotrigermane. In the case of the addition of the Grignard reagent, the resulting germyl Grignard reagent undergoes a facile ligand exchange reaction.Key words: digermene, germylene, Grignard reagents, alkyllithium reagents, germylmagnesium compounds, germyllithium compounds.

Grignard reagent formation via C-F bond activation: a centenary perspective

2022 ◽  
Author(s):  
Eunsung Lee ◽  
Ewa Pietrasiak
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Grignard Reagent ◽  
Bond Activation ◽  
Grignard Reagents ◽  
Bond Dissociation ◽  
High Bond

Examples of Grignard reagents obtained by C-F bond activation with magnesium kept appearing in the literature over the last century. Due to the high bond dissociation energy of the C-F...

Diastereoselective Synthesis of Morpholine Derivatives from Grignard Reagents and N-Sulfinyl Imines

Synlett ◽  
2021 ◽  
Author(s):  
Eric P. A. Talbot ◽  
Joseph M. Bateman ◽  
Diana Chan ◽  
Mustafa Moroglu ◽  
Benjamin Rahemtulla
Keyword(s):  
Grignard Reagent ◽  
Stereoselective Synthesis ◽  
Grignard Reagents ◽  
Diastereoselective Synthesis ◽  
Step Process ◽  
Diastereoselective Addition ◽  
Morpholine Derivatives

The stereoselective synthesis of C3-substituted morpholine derivatives has been achieved through a two-step process involving diastereoselective addition of a Grignard reagent to a sulfinyl imine, followed by cyclization.

Optically active sulfoxides by enantiospecific reactions of bromovinyl aryl sulfoxides with grignard reagents

1992 ◽  
Vol 33 (35) ◽  
pp. 5121-5124 ◽  
Author(s):  
Cosimo Cardellicchio ◽  
Vito Fiandanese ◽  
Francesco Naso ◽  
Antonio Scilimati
Keyword(s):  
Optically Active ◽  
Grignard Reagents
Sign in / Sign up

Export Citation Format

Share Document