68669-68-1

Upstream product

• 917-64-6 methyl magnesium iodide 
• 139214-53-2 2-phenyl-2-(trimethylsilylmethyl)-1,3-dithiane 
• 5769-02-8 2-methyl-2-phenyl[1,3]dithiolane 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 917-54-4 methyllithium 
• 118297-82-8 (Z)-1-phenyl-2-(trimethylsilyl)vinyl diphenyl phosphate 
• 130837-36-4 (E)/(Z)-2-methyl-2-phenyl-1-trimethylsilyl-1-trimethylstannylethene 
• 75-77-4 chloro-trimethyl-silane 
• 676-58-4 methylmagnesium chloride 
• 536-74-3 phenylacetylene 
• 16029-98-4 trimethylsilyl iodide 
• 544-97-8 dimethyl zinc(II) 
• 2612-42-2 (dibromomethyl)trimethylsilane 
• 98-86-2 acetophenone 

Downstream Products

• 18027-28-6 trimethyl(2-phenylpropyl)silane 
• 33632-82-5 trimethyl[(2R)-2-phenylpropyl]silane 
• 68669-67-0 (Z)-trimethyl(2-phenylprop-1-en-1-yl)silane 

Relevant academic research and scientific papers

Nickel-catalysed Coupling of Dithioacetals with Silylmethylmagnesium Chloride. A Simple Synthesis of Allylsilanes

Allylsilanes are conveniently synthesized from the reaction of dithioacetals of ketones with trimethylsilylmethylmagnesium chloride.

Geometric E→Z Isomerisation of Alkenyl Silanes by Selective Energy Transfer Catalysis: Stereodivergent Synthesis of Triarylethylenes via a Formal anti-Metallometallation

An efficient geometrical E→Z isomerisation of alkenyl silanes is disclosed via selective energy transfer using an inexpensive organic sensitiser. Characterised by operational simplicity, short reaction times (2 h), and broad substrate tolerance, the reaction displays high selectivity for trisubstituted systems (Z/E up to 95:5). In contrast to thermal activation, directionality results from deconjugation of the π-system in the Z-isomer due to A1,3-strain thereby inhibiting re-activation. The structural importance of the β-substituent logically prompted an investigation of mixed bis-nucleophiles (Si, Sn, B). These versatile linchpins also undergo facile isomerisation, thereby enabling a formal anti-metallometallation. Mechanistic interrogation, supported by a theoretical investigation, is disclosed together with application of the products to the stereospecific synthesis of biologically relevant target structures.

The efficient method for the preparation of alkenylsilanes from organoaluminums

Silyl esters of sulfonic acids are convenient and efficient silylating agents for β,β- and β-substituted 1-alkenylaluminums. The reaction proceeds at room temperature in CH2Cl2 or hexane for 18 h to give corresponding alkenylsilanes in high yield. At the same time, α,β-disubstituted and α,β,β-trisubstituted 1-alkenylaluminums were inert in the reaction under study. The reaction with aluminacyclopen-2-enes and aluminacyclopentanes takes place on the less sterically hindered reaction center. Using electron-donating solvents (diethyl ether, THF) inhibits the reaction. A new convenient procedure of silylation was developed, which consists in obtaining the silyl tosylate by the reaction of chlorosilanes with anhydrous sodium tosylate in toluene solution. The resulting reaction mixture was reacted with organoaluminum compounds without isolation of silyl tosylate.

Chromium-catalyzed arylmagnesiation of alkynes

Equation presented Arylmagnesiation of unfunctionalized alkynes in the presence of catalytic amounts of chromium(II) chloride and pivalic acid proceeds with high stereoselectivity. The alkenylmagnesium intermediate reacts with various electrophiles to afford the corresponding tetrasubstituted olefins in good yields.

Pd-catalyzed selective tandem arylation-alkylation of 1,1-dihalo-1-alkenes with aryl- and alkylzinc derivatives to produce α-alkyl-substituted styrene derivatives

Trans -selective monoarylation of 1,1-dibromo- and 1,1-dichloro-1-alkenes (1) can be achieved in >80% yields and in ≥98-99% stereoselectivity with arylzinc bromides in the presence of a catalytic amount of Cl2Pd(DPEphos) or Cl2Pd(dppb), the former permitting cleaner and higher yielding reactions. Although THF is a generally satisfactory solvent, ether and toluene are superior to THF in some cases. The second substitution of (Z)-α-bromostyrenes (3) with alkylzincs in the presence of 2 mol% of Pd(t Bu3P)2 proceeds to give the corresponding 2 in >90% yields and in ≥98-99% stereoselectivity. Although somewhat less satisfactory, the use of Cl2Pd(DPEphos) permits a one-pot tandem arylation-alkylation.

Alkylidenation of carbonyl compounds with gem-dizincioalkanes mediated with titanium dichloride

Olefination of carbonyl compounds with gem-dizincio-alkanes, bis(iodozincio)methane, 1,1-bis(iodozincio)ethane, and bis(bromozincio)methyltrimethylsilane, afforded the corresponding olefins in good to excellent yields.

Pd-catalyzed coupling reaction of acetylenes, iodotrimethylsilane, and organozinc reagents for the stereoselective synthesis of vinylsilanes

The reaction of terminal acetylenes with Me3SiI (1) and organozinc reagents in the presence of Pd(PPh3)4 results in addition of the trimethylsilyl group of 1 and an alkyl group of the organozinc reagent to the acetylenes.

STUDIES ON THE SYNTHETIC USE OF STEREODEFINED OLEFINS WITH GEMINAL TRIMETHYLSILYL AND TRIMETHYLSTANNYL SUBSTITUENTS

The synthetic use of 2-alkyl and 2-(hetero)aryl substituted (Z)- and (E)-1-trimethylsilyl-1-trimethylstannylethenes of general formula (Z)-2, (E)-2, (Z)-3 and (E)-3, via the corresponding 1-silylethenyllithiums prepared by tin-lithium exchange reactions a

The Effect of the Ring Size of the Dithiolato Leaving Group on the Orientation of β-Elimination in the Nickel-catalysed Alkenation of Cyclic Dithioacetals with Me3SiCH2MgCl

The product distribution (allyl- vs. vinyl-silanes) of the reactions of dithioacetals derived from alkyl aryl ketones with Me3SiCH2MgCl surprisingly depends on ring size of the cyclic dithioacetals, the five-membered ring substrates affording allylsilane as the major product while the six-membered analogues yield vinylsilanes predominantly.These results indicate that the leaving group, dithiolato moiety, may remain coordinated to the metal centre during the course of the catalytic process.

STEREOSELECTIVE SYNTHESIS AND CHARACTERIZATION OF 2-ALKYL AND 2-(HETERO)ARYL SUBSTITUTED (Z)- AND (E)-1-TRIMETHYLSILYL-1-TRIMETHYLSTANNYLETHENES

The regio- and stereoselective syntheses of the (Z)- and (E)-stereoisomers of some 1-trimethylsilyl-2-(hetero)arylethenylstannanes and 1-trimethylsilyl-2-alkylethenyltrimethylstannanes of general formula (Z)-2, (E)-2, (Z)-3, and (E)-3, respectively, are reported.The strategy followed to prepare (Z)-2, (E)-2, and (E)-3, involves: a) stereoselective cis- and trans-hydroalumination of the corresponding 1-alkynylsilanes; b) conversion of the stereodefined 1-alkenyl-1-silylalanes so obtained into the corresponding aluminates; and c) the cuprous iodide-triethyl phosphite complex mediated reaction of these aluminates with trimethyltin chloride.Compounds (Z)-3, have been prepared by carbocupration of ethynyltrimethylsilane, 12, followed by treatment with trimethyltin chloride.Compounds (Z)-2, (E)-2, (Z)-3, and (E)-3, have been characterized by MS spectrometry and 1H NMR spectroscopy and their configuration has been unambiguously assigned by 119Sn NMR spectroscopy.The results of an attempt to syntesize a 2-alkyl substituted (E)-1-trimethylsilyl-1-trimethylstannyl-2-arylethene are also discussed.