19980-35-9

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 10409-46-8 2-chloro-2-methylcyclohexanone 
• 583-60-8 2-Methylcyclohexanone 
• 43112-38-5 3-(trimethylsilyl)-2-oxazolidinone 
• 2857-97-8 trimethylsilyl bromide 
• 4071-88-9 trimethylsilanyl-acetic acid ethyl ester 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 3167-56-4 trimethylsilyl fluorosulfonate 
• 10416-59-8 N,O-bis-(trimethylsilyl)-acetamide 
• 31469-15-5 1-methoxy-2-methyl-1-trimethylsiloxy-1-propene 
• 7449-74-3 N-methyl-N-trimethylsilylacetamide 
• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 
• 16029-98-4 trimethylsilyl iodide 
• 19980-33-7 6-methyl-1-trimethylsiloxycyclohex-1-ene 

Downstream Products

• 27943-50-6 2-methyl-2-(2-oxopropyl)cyclohexanone 
• 10409-47-9 2-bromo-2-methylcyclohexanone 
• 60415-92-1 2-methyl-2-(2-oxobutyl)cyclohexanone 
• 344408-57-7 2-methyl-2-(1-methyl-2-oxopropyl)cyclohexanone 
• 54322-98-4 (2RS,1'RS)-2-((Hydroxyphenyl)methyl)-2-methylcyclohexanone 
• 54322-98-4 (2RS,1'SR)-2-((Hydroxyphenyl)methyl)-2-methylcyclohexanone 
• 69843-62-5 2-Methoxymethyl-2-methylcyclohexanon 
• 71899-08-6 2-Methyl-2-(1-phenyl-ethyl)-cyclohexanone 
• 132654-04-7 3-(1-Methyl-2-oxo-cyclohexyl)-3-phenyl-propionic acid 
• 58625-69-7 3-(1-methyl-2-oxo-cyclohexyl)-propionic acid 
• 88222-59-7 2-Methyl-2-(tetrahydro-2H-pyran-2-yl)-1-cyclohexanon 
• 10316-61-7 2-(hydroxymethyl)-2-methylcyclohexanone 
• 116859-06-4 E-2-methyl-2-(3'-methoxy-2'-p-tolylthioprop-2'-enyl)cyclohexan-1-one 
• 116859-06-4 Z-2-methyl-2-(3'-methoxy-2'-p-tolylthioprop-2'-enyl)cyclohexan-1-one 

Relevant academic research and scientific papers

Enolate-Based Regioselective Anti-Beckmann C-C Bond Cleavage of Ketones

The Baeyer-Villiger or Beckmann rearrangements are established methods for the cleavage of ketone derivatives under acidic conditions, proceeding for unsymmetrical precursors selectively at the more substituted site. However, the fragmentation regioselectivity cannot be switched and fragmentation at the less-substituted terminus is so far not possible. We report here that the reaction of ketone enolates with commercial alkyl nitrites provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to the otherwise unavailable "anti-Beckmann"cleavage at the less-substituted side chain, while cleavage of thermodynamic enolates of the same ketones represents an alternative to the Baeyer-Villiger oxidation or the Beckmann rearrangement under basic conditions. The method is suited for the transformation of natural products and enables access to orthogonally reactive dicarbonyl compounds.

METHOD FOR PRODUCING SILYLENOL ETHERS

The present invention provides a method for producing a silyl enol ether compound, which is convenient, has highly broad utility and places a low environmental load (less waste). The present invention relates to a method for producing silyl enol ether compound (3), including reacting ketone or aldehyde compound (1) with allylsilane compound (2) in the presence of a base and 0.00001 to 0.5 equivalents of an acid catalyst relative to ketone or aldehyde compound (1), wherein R1 is a hydrogen atom, an alkyl group, an aryl group or the like; R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or the like; R1 and R3, R1 and R2, or R2 and R3 optionally form a ring, together with the carbon atom(s) bonded thereto; R4 , R5 and R6 are each a hydrogen atom, an alkyl group or the like; two of R4, R5 and R6 optionally form a ring; R7, R8, R9, R10 and R11 are each a hydrogen atom, an alkyl group or the like; two of R7, R8, R9, R10 and R11 optionally form a ring.

Facile isomerization of silyl enol ethers catalyzed by triflic imide and its application to one-pot isomerization-(2 + 2) cycloaddition

A triflic imide (Tf2NH) catalyzed isomerization of kinetically favourable silyl enol ethers into thermodynamically stable ones was developed. We also demonstrated a one-pot catalytic reaction consisting of (2 + 2) cycloaddition and isomerization. In the reaction sequence, Tf2NH catalyzes both of the reactions.

Palladium-catalyzed cross-coupling of cyclopropanols with aryl halides under mild conditions

Intra- and intermolecular palladium-catalyzed cross-coupling of cyclopropanols with aryl halides can be achieved in good yields under mild conditions.

Enantioselective decarboxylative alkylation reactions: Catalyst development, substrate scope, and mechanistic studies

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. Sly as a PHOX: The development of an enantioselective decarboxylative palladium-catalyzed allylic alkylation reaction, utilizing phosphinooxazoline ligands, is described. The catalyst is applied to a range of allyl enol carbonate, silyl enol ether, and allyl β-ketoester substrates to provide alkylated ketone products in excellent yield and good ee (see scheme). The utility of these products is demonstrated by their use in several asymmetric syntheses. Mechanistic studies are reported suggesting an unusual inner-sphere mechanism. Copyright

Efficient control for the cationic platinum(II)-catalyzed concise synthesis of two types of fused carbocycles with angular oxygen functionality

Double trouble: An efficient method for the preparation of two types of synthetically useful bicyclo[5.4.0]undecanes with an angular oxygen functionality was realized starting from easily available substrates; this method was based on the [3+2] cycloaddit

Mechanistic studies on α-trifluoromethylation of ketones via silyl enol ethers and its application to other carbonyl compounds

(Chemical Equation Presented) Synthesis of α-CF3 carbonyl compounds has been recognized to be difficult up to now because the polarization of CF3δ--Iδ+ is opposite to that of CH3δ+-Iδ-, and this makes it difficult to introduce CF3+ unit to enolates. We recently reported an effective R-trifluoromethylation of ketones by using Et 2Zn with Rh catalyst, but the mechanism has not fully been cleared. Now, we carried out the detailed mechanistic studies and found the involvement of a highly reactive alkylrhodium complex which derived from Et2Zn and RhCl(PPh3)3 in this α-trifluoromethylation. Furthermore, this α-trifluoromethylation was applied to other types of carbonyl compounds in good yields.

CuBr-catalyzed reaction of N,N-dimethylanilines and silyl enol ethers: An alternative route to β-arylamino ketones

Image Presented A wide range of silyl enol ethers undergo the reactions with N,N-dimethylanilines in the presence of transition metal catalysts under mild conditions to give β-arylamino ketones. In the cases of silyl enol ethers derived from unsymmetrical ketones, regiospecific addition of carbonyl compounds was obtained at the olefinic position of silyl enol ether.

Asymmetric synthetic access to the hetisine alkaloids: Total synthesis of (+)-nominine

A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed, illustrated by a concise asymmetric total synthesis of (+)-nominine (7). The approach relies on an early-stage intramolecular 1,3-dipolar cyclo-addition of a 4-o

Chiral and achiral lithium amides having a fluorous ponytail: Preparation and evaluation as a recycling reagent for lithium enolate generation

Diisopropylamine derivatives bearing a perfluoroalkyl chain were prepared and converted to the corresponding lithium amides by treatment with n-butyllithium. The fluorous lithium amides reacted with ketones to efficiently produce lithium enolates. Asymmetric deprotonation of prochiral ketones was also studied using lithium amides derived from chiral fluorous amines, which gave optical yields comparable with the parent nonfluorous chiral lithium amides. These reusable fluorous amines can be easily recovered by liquid-liquid extraction or chromatographic separation. Georg Thieme Verlag Stuttgart.