97072-45-2

Upstream product

• 100-52-7 benzaldehyde 
• 16212-05-8 (allylsulfonyl)benzene 
• 5324-64-1 2-(benzenesulfonyl)ethynylbenzene 
• 1826-67-1 vinyl magnesium bromide 

Downstream Products

• 67946-07-0 (Z)-(2-vinyloct-1-en-3-(p-tolyl)-1-yl)benzene 
• 16939-57-4 (E)-buta-1,3-dienylbenzene 
• 31915-94-3 (Z)-1-Phenylbuta-1,3-diene 
• 24182-36-3 [(1Z)-2-bromobuta-1,3-dien-1-yl]benzene 

Relevant academic research and scientific papers

Three types of products by carbon nucleophiles toward methoxyphenylacetylenic sulfones

Methoxy-arylacetylenic sulfones were examined to react with various carbanion nucleophiles to result in the three types of products; thus, (i) nucleophiles (MeLi·LiBr, Vinyl MgBr, LiCH2CN) showed the α-addition, however, (ii) Li-CC-TMS afforded β-addition (conjugate addition) products. The (iii) displacement reaction through α-addition/ isomerization/trans-elimination was enhanced by the presence of ortho-methoxy group at high temperature. The heteroatom nucleophiles (nitrogen, oxygen or sulfur atom) in a protic solvent provided only conjugate addition products as reported.

Stereoselective synthesis and reactivity of dienyl zirconocene derivatives

Stereoselective dienyl zirconocene derivatives have been prepared via a tandem allylic C-H bond activation isomerization-elimination reaction. These reagents can be either trapped directly with electrophiles or transmetalated to copper to participate in s

New reactions of γ-halocarbanions: Underestimated reactive intermediates in organic synthesis

Short-lived γ-halocarbanions can be trapped by active electrophiles such as aldehydes, imines, and Michael acceptors to give anionic adducts, which undergo intramolecular substitution to give substituted tetrahydrofurans, pyrrolidines, and cyclopentanes. This has underlain a new method for the synthesis of these valuable ring systems. We have determined the acidity of the γ-halocarbanion precursors and have shown that the halogen atoms in the γ-position relative to the carbanion center exert a significant stabilizing effect on the carbanion.

Stereoselective Preparation of Dienyl Zirconocene Complexes via a Tandem Allylic C-H Bond Activation-Elimination Sequence

Several dienyl zirconocene derivatives were easily prepared, as unique geometrical isomers, from simple non-conjugated unsaturated enol ethers with (1-butene)ZrCp2 complexes. This new methodology is based on a tandem allylic C-H bond activation-elimination sequence and the mechanism has been mapped out by deuterium labeling experiments. The stereochemical outcome of this process was determined by addition of several electrophiles. Moreover, when the organometallic derivative is vinylic as well as allylic such as in 44-47Zr, an unexpected reversal of the stereochemistry has been found during the zirconium to copper transmetalation step.

Base-induced reactions of 3-phenylsulfonylpropyl- and 3-cyanopropyltrimethylammonium chlorides with aldehydes: New synthesis of substituted butadienes

3-Phenylsulfonylpropyltrimethylammonium chloride and 3-cyanopropyltrimethylammonium chloride react with aromatic aldehydes in the presence of excess of potassium tert-butoxide and methyl iodide to give 1,2-disubstituted 1,3-butadienes.

New reactions of γ-halocarbanions: Simple synthesis of substituted tetrahydrofurans

The treatment of 4-chlorobutyronitrile, 3-chloropropyl phenyl sulfone, and other related compounds with a base afforded γ-halocarbanions that undergo fast intramolecular substitution of the halogen to produce substituted cyclopropanes. We found that these short-lived carbanionic intermediates can be trapped with active external electrophilic partners, such as aldehydes, to give the aldol anions. These anions then undergo rapid intramolecular substitution of chloride to produce 2,3- disubstituted tetrahydrofurans. Under the right conditions, yields of tetrahydrofurans are excellent. Similar reactions with ketones gives 2,2,3-trisubstituted furans, but this process is usually less efficient. Ratios between the rates of intramolecular and intermolecular processes were qualitatively estimated by competitive experiments. It was shown that y-halo and y-trimethylammonium substituents substantially increase the kinetic CH acidity of alkane nitriles and sulfones.