40595-35-5Relevant articles and documents
Nickel-Mediated Enantiospecific Silylation via Benzylic C-OMe Bond Cleavage
Balakrishnan, Venkadesh,Murugesan, Vetrivelan,Chindan, Bincy,Rasappan, Ramesh
, p. 1333 - 1338 (2021/02/20)
Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C-C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.
METHOD FOR PRODUCING ALLYLSILANE COMPOUND
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Paragraph 0027; 0029; 0031; 0043, (2017/09/19)
PROBLEM TO BE SOLVED: To provide a method for producing an allylsilane compound which can efficiently produce an allylsilane compound. SOLUTION: An allylsilane compound can be efficiently produced by the reaction between a halogenated allyl compound and a disilane compound in the presence of a palladium element-containing nanoparticle having solvent coordinated on the surface. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2017,JPOandINPIT
N-Heterocyclic Carbene Complexes Of Metal Imido Alkylidenes And Metal OXO Alkylidenes, And The Use Of Same
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Paragraph 0161, (2017/03/21)
The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.
Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates
Cai, Guilong,Zhou, Zhibing,Wu, Wenchao,Yao, Bo,Zhang, Shaowen,Li, Xiaofang
, p. 8702 - 8706 (2016/10/03)
Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates has been developed for efficient synthesis of various allyltrimethylsilanes. The cross-coupling reaction was conducted at room temperature with low catalyst loading of either Pd(PPh3)4 or Pd(PPh3)2Cl2, and exhibited high efficiency and a broad substrate scope. In combination with the cross-coupling by the Lewis-acid catalyzed Hosomi-Sakurai reaction, a novel three-component one-pot cascade reaction was then accomplished to deliver homoallylic alcohols and ethers with high regioselectivity and diastereoselectivity. The three-component reaction defined the yttrium complex as a novel one-carbon synthon, which could either trigger bifunctionalization of alkenes or link two electrophiles and would find applications in organic synthesis.
Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides
Johnson, Keywan A.,Biswas, Soumik,Weix, Daniel J.
supporting information, p. 7399 - 7402 (2016/05/24)
An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2′-bipyridine) that is both air- and moisture-stable over a period of months was introduced.
Rhodium(II)-catalyzed stereoselective synthesis of allylsilanes
Guptill, David M.,Cohen, Carolyn M.,Davies, Huw M. L.
, p. 6120 - 6123 (2014/01/17)
The rhodium-catalyzed decomposition of 2-(triisopropylsilyl)ethyl aryl- and vinyldiazoacetates results in the stereoselective formation of Z-allylsilanes. The transformation is considered to proceed by silyl-directed intramolecular C-H functionalization to form a β-lactone intermediate followed by a silyl-activated extrusion of carbon dioxide.
Pd-catalyzed synthesis of allylic silanes from allylic ethers
Moser, Ralph,Nishikata, Takashi,Lipshutz, Bruce H.
supporting information; experimental part, p. 28 - 31 (2010/03/03)
Chemical Equation Presented Allylic phenyl ethers serve as electrophiles toward Pd(O) en route to a variety of allylic silanes. The reactions can be run at room temperature in water as the only medium using micellar catalysis
Nickel and Palladium Catalysed Coupling of Vinyl Selenides with Trimethylsilylmethylmagnesium Chloride: A New Synthesis of Allyl Silanes
Hevesi, Laszlo,Hermans, Bernard,Allard, Christophe
, p. 6729 - 6730 (2007/10/02)
A new access to allyl silanes by the Ni and Pd catalysed cross-coupling reactions of vinyl selenides and trimethylsilylmethylmagnesium chloride (DME/Rfx/65-83percent yield) is reported.
Palladium-Catalyzed Silylation of Allylic Acetates with Hexamethyldisilane or (Trimethylsilyl)tributylstannane
Tsuji, Yasushi,Kajita, Satoshi,Isobe, Shinya,Funato, Masahiro
, p. 3607 - 3608 (2007/10/02)
Various allylic acetates (1a-j) are silylated with hexamethyldisilane (Me3SiSiMe3, 2) in the presence of a catalytic amount of Pd(DBA)2 and LiCl at 100 deg C to afford the corresponding allylic silanes in high yields.In addition, (trimethylsilyl)tributylstannane (Me3SiSnBu3, 3) can be used for the silylation of aromatic allylic acetates 1g-j at room temperature.
Stereoselective Synthesis of (E)- and (Z)-2-Alkenyltrimethylsilanes from 1,2-Epoxy-1,3-bis(trimethylsilyl)propane
Shimizu, Nobujiro,Imazu, Sachiko,Shibata, Fumihiro,Tsuno, Yuho
, p. 1122 - 1128 (2007/10/02)
Stereoselective synthesis of various (E)- and (Z)-2-alkenyltrimethylsilanes (RCH=CHCH2SiMe3; R=Me, Et, n-Bu, i-Pr, c-hexyl, t-butyl, and phenyl) has been accomplished by a reaction of 1,2-epoxy-1,3-bis(trimethylsilyl)propane with Grignard reagents (RMgX) followed by subsequent Peterson olefination reactions of resulting 1,2-bis(trimethylsilyl)-3-alkanols ; the acid (BF3OEt2 or HClO4)-catalyzed olefination yields the (E)-isomer, while the base (KH or NaH)-induced olefination yields the (Z)-isomer in more than 95 percent stereochemical purity in most cases.
