71092-48-3

Upstream product

• 70901-64-3 trimethyl(2-methylenebut-3-enyl)silane 
• 292638-85-8 acrylic acid methyl ester 

Downstream Products

• 71092-50-7 methyl 4-methylenecyclohexane carboxylate 
• 7299-42-5 δ-terpineol 
• 71092-53-0 2-(4-Trimethylsilanylmethyl-cyclohex-3-enyl)-propan-2-ol 

Relevant academic research and scientific papers

Fluorination process

Compounds of formula (II), (IIIa) or (IIIb) (variables are described in the specification) are prepared by fluorination of β,γ-unsaturated alkyl silanes. These compounds are useful as building blocks in the pharmaceutical industry.

Tandem Transformations Involving Allylic Silanes. 2. Highly Diastereoselective Substitutions Involving [(Trialkylsilyl)methyl]cyclohexene Derivatives with Aldehydes. Synthetic Studies on the Problem of Lewis Acid-Promoted Protodesilylation and Enolization

Diels-Alder cycloaddition of 2-[(trialkylsilyl)methyl]-1,3-butadienes with a variety of dienophiles and substitution reactions between these allylsilane-containing adducts and aldehyde or acid chloride electrophiles have been combined into "tandem sequential reactions." These tandem sequences proceed with equal or greater yield (50-80%) than the reactions performed separately with no decrease in regio- or stereoselectivity. The sequence produces cyclic compounds with three or four stereogenic centers with good to excellent diastereoselectivity from three simple, noncyclic, and achiral reaction partners. Unprecedented levels of diastereoselectivity (de >93%) have been achieved in allylic substitution reactions involving substituted [(trialkylsilyl)methyl]cyclohexene derivatives with aldehyde electrophiles. During the course of these studies, protodesilylation of allylsilanes has been investigated in detail, and a cocatalyst system of TiCl4 and Me2AlCl has been developed that has eliminated silicon loss in the substitution reactions studied. Lewis acid-promoted enolization of ester and ketone substrates with chiral centers adjacent to the carbonyl moiety has been studied also. It has been shown that this event in our studies occurs primarily during catalyst quench. This isomerization is prevented by quenching the catalyst with a Lewis base, such as methanol or triethylamine, prior to aqueous workup.

CHEMISTRY OF THE ORGANOSILICON COMPOUNDS-165 2-TRIMETHYLSILYL-METHYL-1, 3-BUTADIENE-A VERSATILE BUILDING BLOCK FOR TERPENE SYNTHESIS

Two types of synthetically useful reactions of 2-trimethylsilylmethyl-1,3-butadiene (7) are discussed.Reactions of 7 with acid chlorides, aldehydes, ketones and acetals activated by a Lewis acid give isoprenylated compounds, while 7 undergoes the Diels-Alder reaction whit dienophiles.High regiospecificity of the reaction qualifies 7 for a versatile building block of terpene synthesis.

HIGHLY REGIOSELECTIVE DIELS-ALDER REACTIONS OF 2-TRIMETHYLSILYLMETHYL-1,3-BUTADIENE CATALYZED BY A LEWIS ACID AND APPLICATIONS TO SYNTHESES OF TERPENES

2-Trimethylsilylmethyl-1,3-butadiene undergoes highly regioselective Diels-Alder reactions with dienophiles such as acrolein and methyl vinyl ketone catalyzed by aluminium chloride in which the "para" isomers are obtained almost exclusively.The adducts are converted readily to a variety of naturally occurring mono and sesquiterpenes.

HIGHLY REGIOSELECTIVE DIELS-ALDER REACTIONS OF 2-TRIMETHYLSILYLMETHYL- AND 2-TRIMETHYLSTANNYLMETHYL-1,3-BUTADIENE

2-Trimethylsilylmethyl and 2-trimethylstannylmethyl-1,3-butadiene undergo facile cycloaddition with dienophiles, and show high regioselectivity with unsymmetrical dienophiles.