58541-15-4

Upstream product

• 67965-28-0 (1-chloroprop-2-enyl)trimethyl silane 
• 73727-44-3 (Z)-trimethyl(3-phenylprop-1-en-1-yl)silane 
• 128084-29-7 1-(trimethylsilyl)-2-(phenylseleno)-3-phenyl-1-propanol 
• 90304-49-7 Trimethyl-(3-phenyl-1-phenylsulfanyl-propyl)-silane 
• 591-50-4 iodobenzene 
• 762-72-1 allyl-trimethyl-silane 
• 1066-54-2 trimethylsilylacetylene 
• 59376-64-6 (2E)-3-(trimethylsilyl)prop-2-en-1-ol 
• 98-80-6 phenylboronic acid 
• 122-78-1 phenylacetaldehyde 
• 17873-08-4 (phenylsulfanylmethyl)trimethylsilane 
• 84673-88-1 (E)-3-bromo-1-(trimethylsilyl)propene 
• 620-05-3 iodomethylbenzene 
• 107399-03-1 (1-Diazo-3-phenyl-propyl)-trimethyl-silane 

Downstream Products

• 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.

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.) .

Preparation, structure, and reactivity of nonstabilized organoiron compounds. Implications for iron-catalyzed cross coupling reactions

A series of unprecedented organoiron complexes of the formal oxidation states -2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)] [Li(OEt2)]2 (3) and [Ph4Fe][Li(Et 2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4) 4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)] 2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4) 2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe-Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C-C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(-2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively.

Cross-coupling of alkyl halides with aryl Grignard reagents catalyzed by a low-valent iron complex

A striking reversal of the usual reactivity pattern of aryl Grignard reagents is observed for reactions in the presence of catalytic amounts of the "bare" ferrate complex [Li(tmeda)]2[Fe(C2H 4)4] (1). Highly reduced iron-magnesium clusters may play a decisive role in the exceptionally facile and chemoselective cross-coupling reaction with alkyl halides (see scheme).

Tetraalkylammonium salt-based catalyst systems for directing Heck-type reactions. Arylation of allyltrimethylsilane

An appropriate selection of the [Pd/base/QX] catalyst systems allows one to direct at will the palladium-catalysed arylation of allyltrimethylsilane towards the formation of either (E)-1-aryl-3-(trimethylsilyl)-1-propene or 3-aryl-1-propene, by preventing

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.

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.

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.

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

Effect of Silica Gel on the Benzenesulfinic Acid Catalyzed Isomerization of Vinylsilanes. Formation of Silyl Benzenesulfinate

A new method for the isomerization of (Z)-vinylsilanes into the E isomers has been developed.In contrast to the facile protodesilylation of vinylsilanes with arenesulfinic acids, use of silica gel as an additive in the reaction of vinylsilanes with benzenesulfinic acid makes possible the selective isomerization of the double-bond geometry by decreasing the rate of the competing protodesilylation.On the basis of the finding that the isomerization proceeds on the surface of the silica gel activated with benzenesulfinic acid and that benzenesulfinic esters such as ethyl, tributylstannyl, and trimethylsilyl benzenesulfinates are also effective as catalysts for the isomerization, the selective isomerization of vinylsilanes was interpreted in terms of the in situ formation of silyl benzenesulfinate bound to a silanol group of the surface of silica gel.