79239-12-6

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 35660-91-4 (E)-1-phenyl-2-buten-1-one 
• 611-70-1 phenyl isopropyl ketone 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 582-62-7 3-methyl-1-phenylbutan-1-one 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 495-41-0 1-phenylbut-2-en-1-one 
• 15681-48-8 lithium dimethylcuprate 

Downstream Products

• 63481-29-8 2-hydroxymethyl-3-methyl-1-phenyl-1-butanone 
• 123315-22-0 3-methyl-1-phenyl-2-(phenylthiotrimethylsilylmethyl)butan-1-one 
• 79256-95-4 3-methyl-1-phenyl-2-trimethylsilylmethylbutan-1-one 
• 79239-02-4 (3,4-dimethylpent-1-en-3-yl)benzene 
• 79239-01-3 4-methyl-2-phenyl-3-trimethylsilylmethylpentan-2-ol 

Relevant academic research and scientific papers

Tying a Molecular Overhand Knot of Single Handedness and Asymmetric Catalysis with the Corresponding Pseudo-D3-Symmetric Trefoil Knot

We report the stereoselective synthesis of a left-handed trefoil knot from a tris(2,6-pyridinedicarboxamide) oligomer with six chiral centers using a lanthanide(III) ion template. The oligomer folds around the lanthanide ion to form an overhand knot complex of single handedness. Subsequent joining of the overhand knot end groups by ring-closing olefin metathesis affords a single enantiomer of the trefoil knot in 90% yield. The knot topology and handedness were confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The pseudo-D3-symmetric knot was employed as an asymmetric catalyst in Mukaiyama aldol reactions, generating enantioselectivities of up to 83:17 er, which are significantly higher than those obtained with a comparable unknotted ligand complex.

β-Diazocarbonyl Compounds: Synthesis and their Rh(II)-Catalyzed 1,3 C?H Insertions

Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl-substituted hypervalent iodine reagents that gives access to unusual β-diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh-catalyzed intramolecular 1,3 C?H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.

Metal-Free Direct C–H β-Carbonyl Alkylation of Heteroarenes with Cyclopropanols Mediated by K2S2O8

Direct C–H β-carbonyl alkylation of heteroarenes under metal-, acid- and photo-catalyst free conditions has been achieved. A wide scope of substrates, such as various substituted quinolines and isoquinolines, pyridines, pyridazine, benzo[d]thiazole and phenanthroline, underwent the β-carbonyl alkylation efficiently via K2S2O8-mediated ring-opening of cyclopropanols. The corresponding β-heteroarylated ketones were obtained in moderate to excellent yields and gram-scale experiments further demonstrated the practicality of this synthetic protocol. The readily available reagents, mild and environmentally benign conditions make the method extremely attractive. The reaction mechanism is also proposed.

Alkyl Ethers as Traceless Hydride Donors in Br?nsted Acid Catalyzed Intramolecular Hydrogen Atom Transfer

A new protocol for the deoxygenation of alcohols and the hydrogenation of alkenes under Br?nsted acid catalysis has been developed. The method is based on the use of either a benzyl or isopropyl ether as a traceless hydrogen-atom donor, and involves an intramolecular hydride transfer as a key step, which is achieved in a regio- and stereoselective manner.

Highly stereoselective oxazaborolidinium ion catalyzed synthesis of (Z)-silyl enol ethers from alkyl aryl ketones and trimethylsilyldiazomethane

Highly stereoselective (Z)-silyl enol ethers were prepared from alkyl aryl ketones and trimethylsilyldiazomethane (TMSD) using an oxazaborolidinium ion catalyst. In addition, ring-expanded silyl enol ethers were successfully constructed from cyclic ketones. Their synthetic utilities were shown by sequential Mukaiyama aldol and [2 + 2]-cycloaddition reactions.

Carbonium Ion Rearrangements Controlled by the Presence of a Silyl Group

γ-Silyl tertiary alcohols rearrange in protic acid with 1,2-shift of hydride, phenyl, or alkyl groups, and loss of the silyl group to give alkenes.The placing of the silyl group thus controls the carbonium ion rearrangement in a preparatively useful way.Methoxycarbonyl groups do not migrate; instead, cyclopropanes are formed, except when the conformation suitable for cyclopropane formation is unattainable.When the alkene product is 2,2-disubstituted, it can be reprotonated under the reaction conditions and does not therefore always survive.This can be avoided by carrying out the reaction using a Lewis acid on the silyl ether.The starting γ-silyl alcohols are prepared by a variety of versatile methods.

CARBONIUM ION REARRANGEMENTS CONTROLLED BY THE PRESENCE OF A SILYL GROUP

Tertiary alcohols with a γ-silyl group (3) generally undergo a simple carbonium ion rearrangement in acid giving a single alkene product (4) with loss of the silyl group.

Some uses of silicon compounds in organic synthesis

1.The amount of γ-phenylthioalkylation of silyl dienol ethers is increased when the triphenylsilyl ether is used in place of the trimethylsilyl ether.Phenylthiomethylation is the least γ-selective carbon electrophile of several tried so far. 2.The acid-catalysed reactions of a range of γ-silyl tertiary alcohols cleanly give rearrangement, in which the silyl group controls the outcome.The reactions are similar in several respects to the rearrangements of the corresponding pinacols, except that the silicon controlled reactions are usually cleaner and give higher yields.The reaction is particularly useful for setting up quaternary carbon atoms.