126361-99-7Relevant academic research and scientific papers
Copper-catalyzed enantioselective allylic substitution with alkylboranes
Shido, Yoshinori,Yoshida, Mika,Tanabe, Masahito,Ohmiya, Hirohisa,Sawamura, Masaya
supporting information, p. 18573 - 18576 (2013/01/15)
The first catalytic enantioselective allylic substitution reaction with alkylboron compounds has been achieved. The reaction between alkyl-9-BBN reagents and primary allylic chlorides proceeded with excellent γ-selectivities and high enantioselectivities under catalysis of a Cu(I)-DTBM-SEGPHOS system. The protocol produces terminal alkenes with an allylic stereogenic center branched with functionalized sp3-alkyl groups. The reaction with a γ-silicon-substituted allyl chloride affords an efficient strategy for the enantioselective synthesis of functionalized α-stereogenic chiral allylsilanes.
Studies on retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Observation of the formation of unusual 3,3-bissilyl enols
Gan, Zubao,Wu, Ya,Gao, Lu,Sun, Xianwei,Lei, Jian,Song, Zhenlei,Li, Linjie
supporting information; experimental part, p. 6928 - 6934 (2012/08/29)
Detailed investigations of the retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes are described. Based on control experiments and NMR studies, rationalizations are proposed for the formation of 3,3-bissilyl enols, unusual compounds that are stable
Rhodium carbene complexes as versatile catalyst precursors for Si-H bond activation
Krueger, Anneke,Albrecht, Martin
scheme or table, p. 652 - 658 (2012/03/08)
Rhodium(III) complexes comprising monoanionic C,C,C-tridentate dicarbene ligands activate Si-H bonds and catalyse the hydrolysis of hydrosilanes to form silanols and siloxanes with concomitant release of H2. In dry MeNO2, selective formation of siloxanes takes place, while changing conditions to wet THF produces silanols exclusively. Silyl ethers are formed when ROH is used as substrate, thus providing a mild route towards the protection of alcohols with H2 as the only by-product. With alkynes, comparably fast hydrosilylation takes place, while carbonyl groups are unaffected. Further expansion of the Si-H bond activation to dihydrosilanes afforded silicones and polysilyl ethers. Mechanistic investigations using deuterated silane revealed deuterium incorporation into the abnormal carbene ligand and thus suggests a ligand-assisted mechanism involving heterolytic Si-H bond cleavage. Ligand-assisted Si-H bond cleavage: Rhodium-catalysed Si-H bond activation provides a methodology for the silyl group to be transferred to oxygen centres, thus providing access to siloxanes and silanols (using H 2O), alkoxysilanes (using ROH) and to polysiloxanes, such as silicones, when using difunctional silanes. The process is pH neutral, avoids sensitive silylating agents and produces H2 as useful and exclusive side product. Copyright
A convenient multigram synthesis of highly enantioenriched methyl 3-silylglycidates
Lowe, Jason T.,Youngsaye, Willmen,Panek, James S.
, p. 3639 - 3642 (2007/10/03)
A multigram scale synthesis of the four stereoisomers of methyl 3-silylglycidates (epoxysilanes) with high enantiopurity is described. Key reactions include a Sharpless asymmetric epoxidation (SAE) of a trans-vinylsilane and an enzymatic resolution of a r
Synthesis and [4 + 2]-annulation of enantioenriched (Z)-crotylsilanes: Preparation of the C1-C13 fragment of bistramide A
Lowe, Jason T.,Panek, James S.
, p. 3231 - 3234 (2007/10/03)
(Chemical Equation Presented) New chiral crotylsilanes that bear a (Z)-olefin geometry were synthesized in high enantiopurity. The reagents participate in [4 + 2]-annulations with aldehydes to give stereochemically complementary pyrans (relative to (E)-crotylsilanes) bearing 2,6-cis-5,6-cis and 2,6-trans-5,6-cis relationships of peripheral functionalities. A stereoselective synthesis of the C1-C13 fragment of bistramide A is also described highlighting this annulation strategy.
Intramolecular radical hydrosilylation - The first radical 5-endo-dig cyclisation
Amrein, Stephan,Studer, Armido
, p. 1592 - 1593 (2007/10/03)
Intramolecular radical hydrosilylations using allyloxy- and propargyloxycyclohexadienylsilanes comprising 5-endo-trig as well as 5-endo-dig processes are presented.
First Catalytic and Enantioselective Synthesis of Silyl and Stannyl Substituted Cyclopropylmethanols
Imai, Nobuyuki,Sakamoto, Katsumasa,Takahashi, Hideyo,Kobayashi, Susumu
, p. 7045 - 7048 (2007/10/02)
Optically active silyl and stannyl substituted cyclopropylmethanols were effectively obtained by the catalytic and enantioselective cyclopropanation of γ-silyl and γ-stannyl substituted allylic alcohols with Et2Zn and CH2I2 in the presence of chiral N,N'-bis(p-nitrobenzenesulfonyl)-1,2-cyclohexanediamine in good enantioselectivites.The absolute configurations of the resulting metallocyclopropanes were unambiguously established.
Synthesis and Radical Induced Ring Opening Reaction of 1-Trialkylsilyl-2-vinylcyclopropanes
Miura, Katsukiyo,Oshima, Koichiro,Utimoto, Kiitiro
, p. 1665 - 1677 (2007/10/02)
A variety of trialkylsilylvinylcyclopropanes were prepared by two different routes: (a) Cyclopropanation of 1-alkenylsilanes and (b) the reactions of 1-bromocyclopropyllithium with trimethylsilyl chloride.Radical induced ring opening reaction of these cyc
THE SYNTHESIS OF 1-BENZYLDIMETHYLSILYL-4-PHENYLTHIO-1,3-BUTADIENE: A NEW DIENE-REGENERABLE DIELS-ALDER SYNTHON
Pegram, J. J.,Anderson, C. B.
, p. 6719 - 6720 (2007/10/02)
1-Benzyldimethylsilyl-4-phenylthio-1,3-butadiene (1), prepared by hydrosilation of propargyl alcohol, oxidation and followed by Wittig-Horner reaction, underwent Diels-Alder reaction with methyl methacrylate.The adduct after oxidation to the sulfone when
