73727-44-3

Upstream product

• 1066-54-2 trimethylsilylacetylene 
• 59376-64-6 (2E)-3-(trimethylsilyl)prop-2-en-1-ol 
• 98-80-6 phenylboronic acid 
• 122-78-1 phenylacetaldehyde 
• 10147-11-2 propargyl benzene 
• 31683-47-3 1-(trimethylsilyl)-3-phenylprop-1-yne 
• 17873-08-4 (phenylsulfanylmethyl)trimethylsilane 
• 620-05-3 iodomethylbenzene 
• 107399-03-1 (1-Diazo-3-phenyl-propyl)-trimethyl-silane 
• 129584-67-4 Trimethylsiloxy-trimethylsilylmethyl-phenylsulphide 
• 67965-28-0 (1-chloroprop-2-enyl)trimethyl silane 
• 61157-30-0 1,1-Bis(trimethylsilyl)-3-phenyl-1-propanol 
• 128084-29-7 1-(trimethylsilyl)-2-(phenylseleno)-3-phenyl-1-propanol 

Downstream Products

• 58541-15-4 trans-1-(trimethylsilyl)-3-phenyl-1-propene 
• 10147-11-2 propargyl benzene 

Relevant academic research and scientific papers

Nickel-Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents

The direct coupling of allylic alcohols with arylboronic acids or their derivatives catalyzed by Ni(cod)2 in the presence of a catalytic amount of base has been developed. A wide variety of allylic substrates or arylboronic acids turned out to be applicable to this catalytic system. The present method does not require the use of ligands for stabilizing the nickel catalyst in most cases or additional activators for activation of allylic alcohols.

Regioselective Allylation of Carbon Electrophiles with Alkenyl-silanes under Dual Catalysis by Cationic Platinum(II) Species

In the presence of catalytic amounts of platinum(II) chloride and silver(I) hexafluoroantimonate, (Z)-alkenylsilanes reacted with various carbon electrophiles (acetals, aminals, carboxylic anhydrides, alkyl chlorides, etc.) at the γ-position to give allylation products. A plausible mechanism for the platinum-catalyzed allylation involves alkene migration of alkenylsilanes to allylsilanes and subsequent allylation of carbon electrophiles, both of which are catalyzed by a cationic platinum(II) species.

Metal-Free Oxidative Decarbonylative Hydroalkylation of Alkynes with Secondary and Tertiary Alkyl Aldehydes

A new, metal-free, radical-mediated oxidative decarbonylative hydroalkylation of various alkynes with secondary and tertiary alkyl aldehydes using di-tert-butyl peroxide (DTBP) as oxidant is presented. This method enables the simultaneous formation of a C C bond and a C H bond through a sequence of decarbonylation, radical addition and protonation, and provides a straightforward route for transforming alkynes into alkenes with high compatibility with both alkynes and alkyl aldehydes. (Figure presented.) .

Platinum-catalyzed allylation of carbon electrophiles with alkenylsilanes

In the presence of catalytic amounts of PtCl2 and AgSbF6, (Z)-alkenylsilanes react with various carbon electrophiles at the γ-position to give allylation products. A plausible mechanism for the Pt-catalyzed allylation involves alkene migration of alkenylsilanes to allylsilanes and subsequent allylation of carbon electrophiles.

Allyl- And Benzylindium Reagents. Carboindation of Carbon-Carbon and Carbon-Nitrogen Triple Bonds

The reaction of unactivated simple terminal alkynes 1 with allylindiums in THF proceeded smoothly to give the corresponding allylation products 2 in good to high yields. This result is in marked contrast to that of the reaction carried out in DMF, where the allylation of unactivated alkynes was very sluggish. The allylic group of the reagent was attached to the internal carbon of the triple bond, and indium was attached to the less substituted terminal carbon, except for the case of TMS substituted acetylenes 1j and 1k in which the allyl group went to the less substituted carbon of the triple bond. The reaction of unactivated simple terminal and certain internal acetylenes with benzylindium in THF proceeded smoothly to afford the corresponding benzylation products 18 in good to high yields. The benzyl group was attached to the less substituted unhindered carbon of the triple bond, and indium was attached to the more sterically congested carbon. The reaction of activated nitriles 3 with allylindiums in THF at 70°C gave the corresponding allylationenamination products 4 in high to excellent yields. This reaction provides a useful method for the synthesis of highly functionalized enamines, which are not easily available via conventional methods. The mechanisms on the above three indation reactions are discussed.

Transformation of α-assisted carbanions into the corresponding trimethylsiloxy derivatives using bis(trimethylsilyl)peroxide

The reaction of bis(trimethylsilyl)peroxide with tlithium derivatives of sulphides and nitriles is reported to give the corresponding O-trimethylsilyl hemithioacetals and cyanohydrins. From these products the carbonyl function can be exposed in acidic media or in the presence of fluoride ions. This methodology provides an attractive route to transform a CH2-X group (X = PhS, MeS or CN) into the corresponding CHO, allowing the preparation of aldehydes that can be considered difficult to prepare such as, for example, formyltrimethylsilane which was generated and trapped in situ using a Wittig reaction.

Acylsilane chemistry. Synthesis of regio- and stereoisomerically defined enol silyl ethers using acylsilanes

The preparation of enol silyl ethers using a carbonyl addition-Brook rearrangement-elimination sequence was studied. The key intermediate α-silyl-β-X-alkoxides could be prepared in several different ways, including the addition of organolithium or hydride reagents to α-X-acylsilanes (path a, using RM with R = alkyl, aryl, vinyl, alkynyl, silyl, stannyl, phosphinyl, and cyano), the addition of α-X-lithium reagents to acylsilanes (path b, X = phenylthio, phenylsulfonyl), or the addition of silyllithium reagents to α-X-ketones (path c, X = phenylthio, alkoxy). All of the reactions gave complete regiocontrol of silyl enol ether formation, and many gave excellent (>99%) stereocontrol as well. The selectivity of the carbonyl addition, silyl rearrangement, and elimination was studied. For path a, when the R group of RM was a poor carbanion stabilizing group the elimination of the intermediate α-silyl-β-X-alkoxides was stereospecific, and there was a large difference in rate between erythro and threo (erythro > threo). When R was a carbanion stabilizing group, such as aryl or alkynyl, the elimination process became nonstereospecific in some cases, and only small differences between threo and erythro were observed. Path b was especially effective with α-sulfonyl lithium reagents, and these reactions gave predominantly E enol silyl ethers (4/1 to 20/1). The addition of organolithium reagents to β-X-acylsilanes (the homologue of path a) was also briefly explored as a synthesis of siloxy-cyclopropanes.

TRIMETHYLSILYLDIAZOMETHANE: A USEFUL REAGENT FOR THE PREPARATION OF (Z)-1-TRIMETHYLSILYL-1-ALKENES

The rhodium(II) pivalate-catalysed decomposition of α-trimethylsilyldiazoalkenes stereoselectivity affords (Z)-1-trimethylsilyl-1-alkenes in good yields.Keywords trimethylsilyldiazomethane; α-trimethylsilyldiazoalkane; (Z)-1-trimethylsilyl-1-alkene; rhodium(II) pivalate; catalytic decomposition

Pyrolysis of 1-(Trimethylsilyl)-1-alkanols. New Carbene Precursors of Silylcarbene and Phenylcarbene

Pyrolysis of bis(trimethylsilyl)phenylmethanol gave (trimethylsilyl)phenylcarbene by the elimination of trimethylsilanol and the products were compared with those of (trimethylsilyl)phenyldiazomethane.Alkylsilylcarbenes obtained from the pyrolyses of 1,1-bis(trimethylsilyl)-1-alkanols afforded vinyltrimethylsilanes in high yields. (Trimethylsilyl)phenylmethanols were found to be excellent precursors of phenylcarbenes and their intramolecular reactions were also studied.