81790-10-5

Usage

Uses

Used in Organic Synthesis:
(2-BROMOALLYL)TRIMETHYLSILANE is used as a synthon for CH2=C?CH2TMS1–3 and CH2=CBrC?H2, allowing the introduction of the 1-trimethylsilylmethylvinyl group to a wide variety of substrates. This makes it a valuable building block in the synthesis of complex organic molecules.
Used in the Synthesis of 1-Trimethylsilylmethyl-Substituted 1,3-Butadienes:
(2-BROMOALLYL)TRIMETHYLSILANE is used as a key intermediate in the synthesis of 1-trimethylsilylmethyl-substituted 1,3-butadienes, which are important compounds in the preparation of various organic materials and pharmaceuticals.
Used in the Preparation of 1-Hydroxymethylvinyl Anion Equivalents:
The Grignard reagent derived from (2-BROMOALLYL)TRIMETHYLSILANE can be used in the ring-opening reaction of 1-butene oxide, followed by desilylative oxidation to yield α-methylene-γ-lactones. This provides further utility of (2-BROMOALLYL)TRIMETHYLSILANE as a 1-hydroxymethylvinyl anion equivalent, i.e., CH2=?C?CH2OH.
Used in the Synthesis of β,γ-Unsaturated Lactones:
(2-BROMOALLYL)TRIMETHYLSILANE can be used in the synthesis of unstable six-membered β,γ-unsaturated lactones through the alcohol from trans-2,3-epoxybutane, offering a route to access these valuable compounds.
Used in Copper-Catalyzed 1,4-Addition Reactions:
(2-BROMOALLYL)TRIMETHYLSILANE demonstrates its versatility in the copper-catalyzed 1,4-addition to typically unreactive mesityl oxide, proceeding smoothly and contributing to the formation of desired products.
Used in the Synthesis of Tertiary Cyclopentanol:
The ethylaluminum dichloride-induced cyclization of the adduct derived from (2-BROMOALLYL)TRIMETHYLSILANE allows for the high-yield synthesis of tertiary cyclopentanol, showcasing its utility in the preparation of complex organic structures.

Preparation

reaction of 2,3-dibromopropene with lithium (trimethylsilyl)cuprate in HMPA at 0°C (63–90%);(2) reaction of 2,3-dibromopropene with trichlorosilane in the presence of trichlorosilane and copper( I) chloride, followed by treatment with methylmagnesium bromide (63–71%).

Purification Methods

It is fractionally distilled through an efficient column. It is flammable. [Trost & Chan J Am Chem Soc 104 3733 1982, Trost & Coppola J Am Chem Soc 104 6879 1982.]

InChI:InChI=1/C6H13BrSi/c1-6(7)5-8(2,3)4/h1,5H2,2-4H3

Upstream product

• 63915-88-8 1-acetoxy-2-bromo-2-propene 
• 65343-66-0 Tris(trimethylsilyl)aluminium 
• 75-16-1 methylmagnesium bromide 
• 82415-86-9 2-bromo-3-trichlorosilylprop-1-ene 
• 513-31-5 2-bromoallyl bromide 
• 917-64-6 methyl magnesium iodide 
• 91899-54-6 (Trimethylsilyl)copper 
• 18000-27-6 trimethylsilyllithium 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 

Downstream Products

• 17891-65-5 2,3-bis(trimethylsilyl)prop-1-ene 
• 122166-28-3 1,1-diphenyl-2-(trimethylsilyl)methyl-2-propen-1-ol 
• 92413-82-6 2-bromo-3-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)propene 
• 92413-82-6 2-bromo-3-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)propene 
• 132474-39-6 2-{4-(tert-Butyl-dimethyl-silanyloxy)-4-[2-(3-trimethylsilanylmethyl-but-3-en-1-ynyl)-phenyl]-but-2-ynyloxy}-tetrahydro-pyran 
• 132934-02-2 1-(1-hydroxy-2-trimethylsilylmethylprop-2-enyl)-2-(4-methoxybut-3-enyl)-4-methoxybenzene 
• 132934-06-6 1-(1-hydroxy-2-trimethylsilylmethylprop-2-enyl)-4-methoxy-2-(4-methylthiobut-3-enyl)benzene 
• 132934-04-4 2-(4-benzyloxybut-3-enyl)-1-(1-hydroxy-2-trimethylsilylprop-2-enyl)-4-methoxybenzene 
• 136276-85-2 (E)-8-Benzenesulfonyl-2-trimethylsilanylmethyl-octa-1,7-dien-3-ol 
• 136276-87-4 (E)-9-Benzenesulfonyl-2-trimethylsilanylmethyl-nona-1,8-dien-3-ol 
• 135619-36-2 1,1,1-Tris-phenylsulfanyl-3-trimethylsilanylmethyl-but-3-en-2-ol 
• 146175-92-0 1-(1-hydroxy-2-trimethylsilylmethylprop-2-enyl)-4-methoxy-2-(4-methylpent-3-enyl)benzene 
• 953049-49-5 1-(2-Bromo-allyl)-4-tert-butyl-cyclohexanol 
• 83650-13-9 3-(1-Trimethylsilylprop-2-en-2-yl)cyclohexanone 

Relevant academic research and scientific papers

SilverCatalyzed Cascade Carboxylation and Cyclization of Trimethyl(2-methylenebut-3-yn-1-yl)silane Derivatives

C-C bond-forming carboxylation and cyclization of trimethyl(2-methylenebut-3-yn-1-yl)silane derivatives and carbon dioxide was developed. Silver catalysts and CsF promoted the reaction to afford the corresponding 2-furanone and 2-pyrone derivatives in goo

Cyclohexyne cycloinsertion in the divergent synthesis of guanacastepenes

The guanacastepenes are a family of 15 diterpenes that share a common 5-6-7 tricyclic core, which is decorated with quaternary centers, unsaturation, hydroxyl and carbonyl groups. Some of these natural products show interesting antimicrobial potency. Their collective structural and biological features have stirred up vibrant activity among organic chemists. Herein, we disclose an account of our studies toward the synthesis of a number of guanacastepenes. The synthetic strategy relies on the use of cyclohexyne in a cycloinsertion reaction to rapidly construct the guanacastepene core. Isolation of a cyclobutenol as intermediate in the cyclohexyne cycloinsertion provided us with the possibility to study further the reactivity of this metastable compound, and we uncovered novel rearrangements and ring-opening reactions. Stereoselective, late-stage oxidative diversification of the carbon scaffold allowed the synthesis of guanacastepenes N and O and paved the way for the synthesis of guanacastepenes H and D. No strain, no gain! Studies toward the synthesis of the guanacastepene family of diterpenes are presented. The synthetic strategy relies on the use of cyclohexyne as the guanacastepene C-ring, which undergoes cycloinsertion to form the tricyclic carbon scaffold. A host of procedures developed for the diversification of the carbon core allowed the synthesis of guanacastepenes N and O and paved the way for the synthesis of guanacastepenes D and H. Copyright

Synthesis of 2,6-cis-disubstituted 4-methylenetetrahydropyrans by oxy-Michael addition

The combination of an 'ene' reaction between a 2-(2-trialkylsilyloxyalkyl) prop-2-enyl(trimethyl)silane and an alk-1-yn-3-one mediated by zinc(II) iodide, and an intramolecular oxy-Michael reaction, provides an efficient synthesis of cis-2,6-disubstituted 4-methylenetetrahydropyrans of interest in the context of a synthesis of bryostatins. The stereoselective formation of (E)-vinylsilanes in the 'ene' reaction is of interest.

Synthesis of the C(1)-C(16) fragment of bryostatins

A synthesis of the C(1)-C(16) fragment 43 of the bryostatins is reported which features a stereoselective equivalent of an 'ene' reaction between the allylsilane 35 and the alkynone 33 and the stereoselective conjugate addition-cyclisation of the dienyl k

Versatile synthesis of bicyclo[9.3.1]pentadecatriene for new bicyclic taxoids

A common carbon skeleton bicyclo[9.3.1]pentadecatriene of taxachitrienes was synthesized in its des-methyl form in short steps. The key step was Nicholas-Hosomi type reaction in the acidic cyclization between ene-yne biscobalthexacarbonyl complex electrophile with allyltrimethylsilane nucleophile. Decomplexation of the biscobalthexacarbonyl was achieved with a tin hydride and NBS in 1,4-cyclohexadiene solvent.

APLICACION DE LA CICLACION DE ALILSILANO-ALDEHIDOS A LA SINTESIS DE ANILLOS DE TAMANO MEDIO

The allylsilane-aldehyde 12a-c, containing a chiral centre, have been been prepared to study their intramolecular cyclization.These compounds cyclized to 6,7 and 8 membered rings containing a second chiral centre.The results indicate that in these cases the chiral centre of the substrates 12a-c have very little influence upon the diastereoselectivity of the cyclization.Palabras clave: alilsilano, ciclacion intramalecular, anillo de tamano medio.

Preparation of a highly functionalized allylsilane for use in three-bond cascade reactions

Preparation of the novel allylsilane, methyl 3-formyl-4-(phenyldimethylsilylmethyl)pent-4-enoate (2) was accomplished in 7 steps from 2,3-dibromopropene. (2) has great potential as an annulating reagent.

Intramolecular palladium-catalyzed trimethylenemethane cycloadditions: Initial studies

The potential application of [3 + 2] cycloadditions to polycarbocycle construction is considerably enhanced by the ability to perform such reactions intramolecularly. The feasibility of such processes is explored in the context of Pd-catalyzed cycloadditions of 2-[(trimethylsilyl)methyl]allyl carboxylates, wherein trimethylenemethane (TMM) precursor fragment (donor) and the electron-deficient olefin (acceptor) is joined by a tether of simple methylene groups of 3,4, 5, and 8 members. Several versatile synthetic routes to these substrates were developed. 2-Bromo-3-(trimethylsilyl)propene proves to be a key reagent for construction of the donor portion. Acceptors bearing esters, cyano groups, and especially sulfones have been examined. The diastereoselectivity of the reaction has been explored both in terms of ring juncture and the diastereofacial selectivity with respect to an oxygen substituent at the allylic position of the acceptor. Excellent cycloadditions to give the bicyclo[3.3.0]octyl and bicyclo[4.3.0]nonyl systems are observed, whereas larger rings cannot be obtained in this series. The choice of catalyst proves critical, the most useful being either tetrakis(triphenylphosphine)palladium and DPPE or, more generally, triisopropyl phosphite and palladium acetate. The first cycloaddition of a 1,1-dialkylated TMM precursor, which fails in intermolecular cases, has been observed in this intramolecular series to give a bridgehead-substituted bicycle. A rationale for the observed diastereoselectivity is presented.

STEREOSELECTIVE SYNTHESIS OF 3-(D-GLYCOPYRANOSYL)PROPENES BY USE OF ALLYLSILANES

Reactions of allylsilanes with methyl pyranosides and pyranosyl chlorides proceeded very smoothly in the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate and iodosilane to give the corresponding glycopyranosyl-3-propenes in highly stereoselective mode.The configuration depends upon the structure of allylsilanes. 2-Bromo-2-propenyltrimethylsilane, the lowest nucleophile among the allylsilanes used, afforded an almost pure C-α-glycosyl compound.