68669-61-4

Basic information

• Product Name: Silane, trimethyl(2-phenyl-1-butenyl)-, (Z)-
• CAS NO: 68669-61-4
• Molecular Formula: C13H20Si
• Molecular Weight: 204.387
• Mol File: 68669-61-4.mol
• Article Data: 7

Chemical Properties

• CAS DataBase Reference: Silane, trimethyl(2-phenyl-1-butenyl)-, (Z)-(CAS DataBase Reference)
• NIST Chemistry Reference: Silane, trimethyl(2-phenyl-1-butenyl)-, (Z)-(68669-61-4)
• EPA Substance Registry System: Silane, trimethyl(2-phenyl-1-butenyl)-, (Z)-(68669-61-4)

Safety Data

• Hazardous Substances Data: 68669-61-4(Hazardous Substances Data)

Upstream product

• 557-20-0 diethylzinc 
• 2170-06-1 1-Phenyl-2-(trimethylsilyl)acetylene 
• 3536-96-7 vinylmagnesium chloride 
• 2039-93-2 1-ethylstyrene 
• 97-93-8 triethylaluminum 
• 39854-50-7 2-ethyl-2-phenyl-1,3-dithiane 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 6008-82-8 2-ethyl-2-phenyl-1,3-dithiolane 
• 74-96-4 ethyl bromide 
• 97607-44-8 1-trimethylsilyl-2-phenyl-2-trimethylstannyl-ethene 
• 68669-62-5 (E)-trimethyl(2-phenylbut-1-en-1-yl)silane 
• 536-74-3 phenylacetylene 

Relevant articles and documents

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.

A Nickel-catalyzed carbozincation of aryl-substituted alkynes

The addition of dialkylzincs or diphenylzinc to substituted phenylacetylenes in the presence of catalytic amounts of Ni(acac)2 in THF:NMP mixtures produces syn-carbozincation products with good to excellent regio- and stereoselectivity. After quenching with an electrophile (iodine, acyl chloride, allyl bromide) tetrasubstituted olefines are obtained in good to satisfactory yields. An intramolecular version of the reaction is possible using a terminal triple bond bearing an iodine at a remote position. More substituted iodo-alkynes furnish only reductive elimination products. An application to a stereoselective synthesis of (Z)-tamoxifen (Z:E > 99:1) has been developed.

Regiospecific and Stereospecific Synthesis of E- and Z-Trisubstituted Alkenes via 2,2-Disubstituted Vinylsilanes

Treatment of terminal alkynes 1 with the organocopper reagents derived from Grignard reagents, cuprous iodide, and lithium bromide (molar ratio 2:1:2) at low temperature followed by the addition of chlorotrimethylsilane gave the 2,2-disubstituted vinylsilanes 2 with complete regio- and stereospecificity (syn addition).Electrophilic substitution of 2 with ICl, Br2, and acetyl chloride gave the corresponding vinyl iodides, bromides, and α,β-unsaturated ketones 5 with retention of configuration.Epoxidation of 2 with MCPBA gave the epoxy silanes 6, which upon treatment with concentrated HX and BF3*Et2O gave the vinyl halides 7 with net inversion of configuration.If the epoxy silanes 6 were first converted to the β-hydroxy silanes 8 by Gilman's reagents, either E- or Z-trisubstituted alkenes 9 and 10 could be obtained by treatment with acid or base.Vinyl halides 7 could also be stereoselectively converted to other functionalities via the vinyllithium intermediates.