42591-54-8

Upstream product

• 6738-06-3 phenylethynylmagnesium bromide 
• 75-78-5 dimethylsilicon dichloride 
• 1004-22-4 (phenylethynyl)sodium 
• 925-90-6 ethylmagnesium bromide 
• 536-74-3 phenylacetylene 
• 87710-79-0 methoxy-dimethyl(phenylethynyl)silane 
• 62593-92-4 phenylethynyl-N,N-diethylaminodimethylsilane 
• 4440-01-1 lithium phenylacetylide 

Downstream Products

• 87710-79-0 methoxy-dimethyl(phenylethynyl)silane 
• 135560-95-1 ((3R,4S,5R,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-2-phenylselanyl-tetrahydro-pyran-3-yloxy)-dimethyl-phenylethynyl-silane 
• 75-77-4 chloro-trimethyl-silane 
• 83838-04-4 Ethynyl-dimethyl-phenylethynyl-silane 
• 168985-21-5 3,4,6-Tri-O-benzyl-2-O--β-D-glucopyranosyl 2-pyridyl sulfone 
• 168985-19-1 3,4,6-Tri-O-benzyl-2-O--α-D-mannopyranosyl 2-pyridyl sulfone 
• 42591-61-7 Dimethyl(phenylethinyl)fluorsilan 
• 886-66-8 1,4-diphenyl-1,3-butadiyne 
• 197159-01-6 3,4,6-Tri-O-benzyl-2-O-[dimethyl(phenylethynyl)silyl]-β-D-glucopyranosyl phenyl sulfone 
• 197159-00-5 3,4,6-Tri-O-benzyl-2-O-[dimethyl(phenylethynyl)silyl]-α-D-mannopyranosyl phenyl sulfone 
• 241812-05-5 2,5-Bis(phenylethynyldimethylsilyl)furan 
• 241812-04-4 2,5-Bis(phenylethynyldimethylsilyl)thiophene 
• 330209-58-0 1,2-bis(phenylethynyldimethylsiloxy)ethane 
• 350831-05-9 (dimethyl-phenylethynyl-silanyloxy)-diphenyl-acetaldehyde 

Relevant academic research and scientific papers

Synthesis of Benzo[c]silole Derivatives Bearing a Tetrasubstituted Exocyclic C=C Double Bond by Palladium-Catalyzed Domino Reactions

The synthesis of diversely substituted 2,3-dihydro-benzo[c]siloles through an unprecedented palladium-catalyzed domino sequence is reported, involving a cyclocarbopalladation of an internal silylalkyne. This reaction proceeds with complete stereoselectivity to lead to a fully substituted exocyclic C=C double bond. Notably, the overall domino sequence appears to be crucial to obtain the desired cyclic vinylsilanes.

Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes

An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.

Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon

The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated.

Iridium-promoted conversion of chlorosilanes to alkynyl derivatives in a one-pot reaction sequence

By making use of the catalytic potential of the iridium system [{Ir(μ-Cl)(CO)2}2]/NEt(i-Pr)2 in the synthesis of silyl-functionalized alkynes via silylative coupling of terminal alkynes/diynes with iodosilanes, we propose

Selective synthesis of functional alkynylmono- and -trisilanes

The selective synthesis of functional alkynylsllanes RC=C(SiMe 2)m,-X (m = 1, 3) was investigated. Monofunctionalization with or without protecting groups gave moderate to good yields of alkynyldimethylmonosilanes RC=CMe2SiX [R = Ph, X = Cl. (1), NEt 2 (2), OMe (3), H (4), Br (5), I (6), Cp (8), C5H 4Li (10), Ph (11); R = Pr, X = Ph (12)]. Compounds 4 and 8 were converted into the (alkyne)transition-metal complexes 4-Cp2Mo 2(CO)4 (13) and 8-Co2(CO)6 (14), respectively, which were characterized by X-ray diffraction. Stepwise extension and functionalization of the silane chain starting from 1chloro-2-(diethylamino) tetramethyldisilane (Et2NMe2Si-SiMe2Cl) yielded the trisilanes Ph-(SiMe2J3-X [X = NEt2 (18), OMe (19), Cl (20), H (21), C=CPh (22), C=CPr (23)]. The synthesized compounds were characterized by NMR and IR spectroscopy, 4, 11, 13, and 14 also by UV/Vis spectroscopy.

1,2-cis-c-glycoside synthesis by samarium diiodide-promoted radical cyclizations

The samarium diiodide reduction of glycosyl pyridyl sulfones bearing a silicon-tethered unsaturated group at the C2-OH position leads to the stereo-specific synthesis of 1,2-cis-C-glycosides in good yield after desilylation. These reactions proceed via an

1,1-Organoboration of Di-1-alkynylsilanes with Alkynyl Groups of Different Reactivity: New Organometallic-Substituted Siloles

The synthesis of alkynyl(trimethylstannyl)ethynyl>dimethylsilanes 4 C: R1 = Bu (b), tBu (c), iPent (d), Ph (e), SiMe3 (f)> is reported.The intermolecular 1,1-ethyloboration of 4 with triethylborane takes place selectively at the Sn-C bond to give first the alkenyl(alkynyl)dimethylsilanes 5 and 6.There exists an equilibrium between 5 and 6, and compound 6 has the suitable stereochemistry for the final intramolecular 1,1-vinyloboration to form the 4-(diethylboryl)-2-(trimethylstannyl)siloles 7.Protodeborylation of 7 with water gives the 2-(trimethylstannyl)siloles 8, and protodeborylation and protodestannylation with an excess of acetylacetone affords the siloles 9.Multinuclear NMR (1H-, 11B-, 13C-, 29Si-, and 119Sn-) serves for monitoring the reactions and for the characterization of the products. - Key Words: Silanes, alkynyl-/ 1,1-Ethyloboration, intermolecular/ 1,1-Vinyloboration, intramolecular/ Siloles/ Protodeborylation/ Protodestannylation

Base cleavage of R-SiMen(OMe)3-n bonds (R m-ClC6H4CH2, PhC, or Cl2CH) and alkoxy exchange in RSiMen(OMe)3-n (R = m-ClC6H4CH2)

The rates of cleavage of R-SiMen(OMe)3-n bonds (n = 0-3) in NaOMe-MeOH have been measured for R = (i) -ClC6H4CH2, (ii) Ph, and (iii) Cl2CH.The relative reactivities as n is varied in the sequence 3, 2, 1, 0 within each series are: (i) 1,7.2, 2.7, 0.13; (ii) 1, 27, 24, 5.5; (iii) 1, 38, 93, 29.These reactivity variations are discussed in terms of opposition between the rate-enhancing polar effects of the OMe groups and a unusual type of steric affect which arises on introduction of OMe in place of Me.The rates of replacement of one OMe group of m-ClC6H4CH2Men(OMe)3-n by an OEt group in EtOH containing a base have also been measured; in this case the rates rise progressively with the value of n, the relative reactivities for n = 2,1, and 0 being 1, 4.4, and 27, respectively.

Base Cleavage of R-Si Bonds of Silanols RSiMe2OH. A Proposed New Mechanism of Substitution at Silicon

Cleavage of R-Si bonds has been found to occur unexpectedly rapidly in solutions of RSiMe2OMe (R = m-ClC6H4CH2 or PhCC) in 5 vol-percent H2O-MeOH containing relatively small concentrations of NaOMe, but with a levelling off of the rate at high concentrations of the base.The behaviour is attributed to the formation of RSiMe2OH and hence RSiMe2O-, and it is suggested that unimolecular dissociation of the silanolate anion RSiMe2O- to give R- and the silianone Me2Si=O (both of which react rapidly with the solvent) plays a significant role.The silanols RSiMe2OH are roughly estimated to have pKa values of 11 (R = m-ClC6H4CH2) and 9.8 (R = PhCC) in water.