129158-82-3Relevant academic research and scientific papers
PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols
McLaughlin, Mark G.,Cook, Matthew J.
supporting information; scheme or table, p. 11104 - 11106 (2011/11/07)
A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl2/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.
Titanocene-mediated homolytic opening of epoxysilanes
Puljic, Nicolas,Albert, Matthias,Dhimane, Anne-Lise,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max
, p. 2297 - 2305 (2007/10/03)
The titanocene(III) chloride mediated opening of silyloxiranes has been examined. Electron transfer from the metal leads to α-silyl radicals with total regiocontrol. The radicals could be trapped by various olefins, and the corresponding adducts were obtained in good yields (Table). Further substitution of the oxirane by alkyl groups proved detrimental to the reactions, but ring opening remained essentially regioselective.
Diastereoselective acyclic aza-[2,3] Wittig sigmatropic rearrangements
Anderson, James C.,Smith, Stephen C.,Swarbrick, Martin E.
, p. 1517 - 1521 (2007/10/03)
The scope of anion-stabilising groups in promoting and controlling the diastereoselection of the aza-[2,3] Wittig sigmatropic rearrangement has been assessed by the syntheses of allylic amines 1c-g that have incorporated SiPhMe2, Ph, SPh, SOPh and SO2Ph respectively at the C-2 position. The subsequent anionic [2,3]-sigmatropic rearrangements are analysed with respect to the extent of diastereoselection of the product homoallylic amines 2 and 3. It appears that silicon not only is the most efficient at electronically facilitating this rearrangement, but its steric bulk controls the diastereoselectivity of the process exclusively. Phenyl and phenylthio substituents also have a similar, but decreased, effect on diastereoselection that mirrors their lower steric bulk in comparison to the silicon derivative. Sulfoxide and sulfone substituents are incompatible with the reaction conditions required for rearrangement.
Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation
Adam, Waldemar,Richter, Markus J.
, p. 3341 - 3346 (2007/10/02)
A direct synthesis of silyl epoxy alcohols from vinylsilanes is described.It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group.The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)4 to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3.Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields.The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results.In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.
Sequential Diastereoselective Addition and Palladium(II)-Catalyzed Allylic Acetate Transposition of syn- and anti-α-Acetoxy-β-silyl-(E)-hex-4-enoates with Achiral Acetals. Asymmetric Synthesis of Differentiated Syn and Anti 1,3-Diol Synthons
Panek, James S.,Yang, Michael,Solomon, Jason S.
, p. 1003 - 1010 (2007/10/02)
syn- and anti-Methyl α-acetoxy-β-(dimethylphenylsilyl)-(E)-hex-4-enoates, (2R,3R)-8a and (2S,3R)-8b, undergo highly diastereo- and enantioselective addition reactions with aldehydes and acetals 11 catalyzed by the action of trimethylsilyl trifluoromethane
Allylsilanes in organic synthesis; convenient preparation of synthetic intermediates by catalytic hydrosilation of acetylenic alcohols
Murphy,Spencer,Procter
, p. 1051 - 1054 (2007/10/02)
Synthetically useful vinylsilane-alcohols such as (1) can be easily prepared by the catalytic hydrosilation of the appropriate acetylenic alcohols in high yield, and with excellent regio- and stereoselectivity, without the need to protect the hydroxyl gro
