147159-44-2

Upstream product

• 1611-78-5 1,3-bis-dimethylaminotrimethinium perchlorate 
• 931-50-0 cyclohexylmagnesium bromide 
• 167900-52-9 2-Allyl-2-[(E)-3-(2-oxo-[1,3]dioxolan-4-yl)-allyl]-malonic acid dimethyl ester 
• 927-80-0 1-ethoxyacetylene 
• 2043-61-0 cyclohexanecarbaldehyde 
• 75-07-0 acetaldehyde 
• 168037-33-0 2-Allyl-2-[(E)-3-(2,2-dimethyl-[1,3]dioxolan-4-yl)-allyl]-malonic acid dimethyl ester 
• 42134-55-4 3-cyclohexyl-2-propen-1-ol 
• 2136-75-6 (triphenylphosphoranylidene)acetaldehyde 
• 97563-45-6 1-cyclohexylprop-2-yn-1-ol 
• 4361-28-8 3-cyclohexylpropanal 
• 6048-09-5 3-cyclohexylacrylic acid ethyl ester 
• 2114-42-3 allylcyclohexane 

Downstream Products

• 865776-62-1 2-amino-5-(2-cyclohexyl-2-methoxy-ethyl)-thiazole-4-carboxylic acid methyl ester 
• 865776-68-7 5-(2-cyclohexyl-2-methoxy-ethyl)-thiazole-4-carboxylic acid methyl ester 
• 865776-74-5 5-(2-cyclohexyl-2-methoxy-ethyl)-thiazole-4-carboxylic acid 
• 1161512-46-4 5-cyclohexyl-2-isoxazoline 
• 1185538-18-4 C₁₉H₂₃NO₃ 
• 1185538-16-2 C₂₀H₂₅NO₄ 
• 1033750-81-0 C₉H₁₅NO 
• 1252007-00-3 C₂₁H₂₈N₂O₄ 
• 17343-88-3 (E)-3-cyclohexyl-acrylic acid ethyl ester 
• 1269823-53-1 (R)-3-(4-(7H-pyrrolo[2,3-c]pyridazin-4-yl)-1H-pyrazol-1-yl)-3-cyclohexylpropanenitrile 

Relevant academic research and scientific papers

1,4-Addition of silicon dienoates to α,β-unsaturated aldehydes catalyzed by in situ-generated silicon Lewis acid

In situ-generated silyl methide species (R3Si-CTf 2R′) effectively catalyzed the reaction of β-substituted α,β-unsaturated aldehydes with silicon dienoates such as 3-bromo-2-TESO-furan to give the corresponding γ-adducts with excelle

Palladium/Copper-catalyzed Oxidation of Aliphatic Terminal Alkenes to Aldehydes Assisted by p-Benzoquinone

The development of an anti-Markovnikov Wacker-type oxidation for simple aliphatic alkenes is a significant challenge. Herein, a variety of aldehydes can be selectively obtained from various unbiased aliphatic terminal alkenes using PdCl2(MeCN)2/CuCl in the presence of p-benzoquinone (BQ) under mild reaction conditions. Isomerization of the terminal alkene to the internal alkene was suppressed via slow addition of the starting material to the reaction mixture. In addition to the Pd catalyst, CuCl and BQ were essential in order to obtain the anti-Markovnikov product with high selectivity. Terminal alkenes bearing a halogen substituent afforded their corresponding aldehydes with high anti-Markovnikov selectivity. The halogen acts as a directing group in the reaction. DFT calculations indicate that a μ-chloro Pd(II)?Cu(I) bimetallic species with BQ coordinated to Cu is the catalytically active species in the case of a terminal alkene without a directing group.

Highly Enantioselective Synthesis of Functionalized Glutarimide Using Oxidative N-Heterocyclic Carbene Catalysis: A Formal Synthesis of (?)-Paroxetine

A simple yet highly effective approach toward enantioselective synthesis of trans-3,4-disubstituted glutarimides from readily available starting materials is developed using oxidative N-heterocyclic carbene catalysis. The catalytic reaction involves a formal [3 + 3] annulation between enals and substituted malonamides enabling the production of glutarimide derivatives in a single chemical operation via concomitant formation of C-C and C-N bonds. The reaction offers easy access to a broad range of functionalized glutarimides with excellent enantioselectivity and good yield. Synthetic application of the method is demonstrated via formal synthesis of (?)-paroxetine and other bioactive molecules.

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst

We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.

Dehydrogenative Synthesis of Linear α,β-Unsaturated Aldehydes with Oxygen at Room Temperature Enabled by tBuONO

Synthesis of linear α,β-unsaturated aldehydes via a room-temperature oxidative dehydrogenation has been realized by the cocatalysis of an organic nitrite and palladium with molecular oxygen as the sole clean oxidant. Linear α,β-unsaturated aldehydes could be efficiently prepared under aerobic catalytic conditions directly from the corresponding saturated linear aldehydes. Besides linear products, the aromatic analogy could also be smoothly achieved by the same standard method. The organic nitrite redox cocatalyst and alcohol solvent play a key role for realizing this method.

Synthesis of 1,3-Amino Alcohols, 1,3-Diols, Amines, and Carboxylic Acids from Terminal Alkynes

The half-sandwich ruthenium complexes 1-3 activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. These reactions are believed to proceed via addition of water to metal vinylidene intermediates (4). The functionalization of propargylic alcohols by metal vinylidene pathways is challenging owing to decomposition of the starting material and catalytic intermediates. Here we show that catalyst 2 can be employed to convert propargylic alcohols to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to propargylic amine derivatives, thereby establishing a route to enantioenriched 1,3-amino alcohol products. We also report the development of formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively, from terminal alkynes. This chemistry expands the scope of products that can be prepared from terminal alkynes by practical and high-yielding metal-catalyzed methods.

HETEROCYCLIC COMPOUNDS AS JANUS KINASE INHIBITORS

The invention provides compounds of formula (I) or a salt thereof as described herein. The invention also provides pharmaceutical compositions comprising a compound of formula (I), processes for preparing compounds of formula (I), intermediates useful for preparing compounds of formula I and therapeutic methods for suppressing an immune response or treating cancer or a hematologic malignancy using compounds of formula (I).

2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone

Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.

AgAsF6 as safe alternative to AgClO4 for generating cationic zirconocene species: Utilities in Lewis acid-promoted selective C---C bond forming reactions

For generating cationic zirconocene species that are useful for organic synthesis, AgAsF6 proved to be an efficient catalyst that serves as a safe alternative to AgClO4. Scope and limitation is discussed on this new catalyst in the processes including (1) alkyl/alkenyl transfer reaction from organozirconocene chloride to aldehyde, (2) two- and four-carbon homologation of aldehyde, (3) dual synthetic methods of 1,3-dienes from aldehydes/ketones via 1,3-bimetallic species, and (4) three-component alkylative cycloaddition via o-quinodimethane species.