6553-64-6

Upstream product

• 108-75-8 2,4,6-trimethyl-pyridine 
• 21690-26-6 6-bromo-2,2-dimethylcyclohexan-1-one 
• 563-80-4 3-methyl-butan-2-one 
• 107-02-8 acrolein 
• 5394-63-8 2,2,6-trimethyl-4H-1,3-dioxin-4-one 
• 115-11-7 isobutene 
• 91056-64-3 6,6-dimethylcyclohex-1-enyl acetate 
• 38309-48-7 6,6-dimethyl-trans-2,3-epoxycyclohexanol 
• 930-68-7 cyclohexenone 
• 74-88-4 methyl iodide 
• 62952-32-3 3-ethoxy-6,6-dimethylcyclohex-2-en-1-one 
• 1073-13-8 4,4-dimethylcyclohexenone 
• 1272341-16-8 C₁₆H₂₄OSi 
• 501443-29-4 3-ethoxy-4,4-dimethylcyclohex-2-en-1-one 

Downstream Products

• 18329-25-4 5-isopropyl-2,2-dimethylcyclohexan-1-one 
• 55337-84-3 4-bromo-6,6-dimethyl-cyclohex-2-enone 
• 99342-65-1 6,6-dimethyl-cyclohex-2-enone-(2,4-dinitro-phenylhydrazone) 
• 144225-48-9 2,2-dimethyl-3-(2-propenyl)cyclohexanone 
• 444809-15-8 1-methoxymethoxymethyl-6,6-dimethyl-cyclohex-2-enol 
• 134655-04-2 5-(2-Iodoethyl)-2,2-dimethylcyclohexan-1-one 
• 134655-05-3 5-(3-Iodopropyl)-2,2-dimethylcyclohexan-1-one 
• 1373048-86-2 (S)-1,6,6-trimethylcyclohex-2-en-1-ol 
• 1629798-35-1 (E)-N-(6,6-dimethylcyclohex-2-en-1-ylidene)-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Reactions of Singlet Oxygen with Enol Esters

Singlet oxygenation of 1-adamantylideneethyl acetate (4) and 6,6-dimethylcyclohex-1-enyl acetate (7) produces only "ene" reaction products.Photooxygenation of Δ1,6-2-oxabicyclodecen-3-one (9), in contrast, yields ene, acyl-shifted, and cycloaddition products.The product distribution resulting from oxidation of 9 indicates that attack of singlet oxygen (1O2) occurs exclusively on the same side of the double bond as the ester functional group.The bimolecular rate constant for reaction of 9 with 1O2 is found to be ca. 50 times larger than those of 4 and 7.These results are explained most economicaly by invoking the ini tial formation of a perepoxide intermediate.In the case of 9, stabilization of the transition state leading to the perepoxide by interaction of the incoming 1O2 molecule with the ester functionally produces the observed rate enhancement and stereospecificity.

Platinum-Catalyzed α,β-Desaturation of Cyclic Ketones through Direct Metal–Enolate Formation

The development of a platinum-catalyzed desaturation of cyclic ketones to their conjugated α,β-unsaturated counterparts is reported in this full article. A unique diene-platinum complex was identified to be an efficient catalyst, which enables direct metal-enolate formation. The reaction operates under mild conditions without using strong bases or acids. Good to excellent yields can be achieved for diverse and complex scaffolds. A wide range of functional groups, including those sensitive to acids, bases/nucleophiles, or palladium species, are tolerated, which represents a distinct feature from other known desaturation methods. Mechanistically, this platinum catalysis exhibits a fast and reversible α-deprotonation followed by a rate-determining β-hydrogen elimination process, which is different from the prior Pd-catalyzed desaturation method. Promising preliminary enantioselective desaturation using a chiral-diene-platinum complex has also been obtained.

Tuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, E-Volkendousin, and E-Guggulsterone

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and Z-selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of E-guggulsterone and E-volkendousin was also claimed using a short sequence.

Enantioselective Synthesis of cis-Decalin Derivatives by the Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones

A novel strategy for the synthesis of cis-decalins by an ytterbium-catalyzed asymmetric inverse-electron-demand Diels–Alder reaction of 2-pyrones and silyl cyclohexadienol ethers is reported here. A broad range of synthetically important cis-decalin derivatives with multiple contiguous stereogenic centers and functionalities are obtained in good yields and stereoselectivities. A full set of diastereomeric substituted cis-decalin motifs are readily accessible by tuning the absolute configurations of substituted silyl cyclohexadienol ethers (R or S) as well as the ligands (R or S). The synthetic potential is showcased by the enantioselective total synthesis of 4-amorphen-11-ol, and further demonstrated by the first total synthesis of cis-crotonin.

11-Step Total Synthesis of (-)-Maoecrystal v

An expedient, practical, and enantioselective route to the highly congested ent-kaurane diterpene maoecrystal V is presented. This route, which has been several years in the making, is loosely modeled after a key pinacol shift in the proposed biosynthesis. Only 11 steps, many of which are strategic in that they build key skeletal bonds and incorporate critical functionalities, are required to access (-)-maoecrystal V. Several unique and unexpected maneuvers are featured in this potentially scalable pathway. Reevaluation of the biological activity calls into question the initial exuberance surrounding this natural product.

Ruthenium Lewis Acid-Catalyzed Asymmetric Diels–Alder Reactions: Reverse-Face Selectivity for α,β-Unsaturated Aldehydes and Ketones

Acrolein, methacrolein, methyl vinyl ketone, ethyl vinyl ketone, 3-methyl-3-en-2-one, and divinyl ketone were coordinated to a cationic cyclopentadienyl ruthenium(II) Lewis acid incorporating the electron-poor bidentate BIPHOP–F ligand. Analysis by NOESY and ROESY NMR techniques allowed the determination of conformations of enals and enones present in solution in CD2Cl2. The results were compared to solid-state structures and to the facial selectivities of catalytic asymmetric Diels–Alder reactions with cyclopentadiene. X-Ray structures of four Ru-enal and Ru-enone complexes show the α,β-unsaturated C=O compounds to adopt an anti-s-trans conformation. In solution, enals assume both anti-s-trans and anti-s-cis conformations. An additional conformation, syn-s-trans, is present in enone complexes. Enantioface selectivity in the cycloaddition reactions differs for enals and enones. Reaction products indicate enals to react exclusively in the anti-s-trans conformation, whereas with enones, the major product results from the syn-s-trans conformation. The alkene in s-cis conformations, while present in solution, is shielded and cannot undergo cycloaddition. A syn-s-trans conformation is found in the solid state of the bulky 6,6-dimethyl cyclohexanone-Ru(II) complex. The X-ray structure of divinyl ketone is unique in that the Ru(II) center binds the enone via a η2bond to one of the alkene moieties. In solution, coordination to Ru–C=O oxygen is adopted. A comparison of facial preference is also made to the corresponding indenyl Lewis acids.

Enzymatic resolution of racemic secondary cyclic allylic alcohols

The resolutions of five racemic cyclic alcohols: 6,6-dimethylcyclohex-2-en-1-ol (±)-5, 4,4-dimethylcyclohex-2-en-1-ol (±)-7, 5,5-dimethylcyclohex-2-en-1-ol (±)-11 and isomeric trans-(±)-13 and cis-piperitols (±)-14 are presented. They were resolved by enzymatic esterification with vinyl esters or by enzymatic hydrolysis of their racemic esters in phosphate buffer. The following lipases were used as biocatalysts: Novozyme 435 (Candida antarctica), Amano PS (Burkholderia cepacia) and lipase from Candida cylindracea. All isomers of alcohols were obtained with at least 96% ee.

Sequential hydroformylation/aldol reactions: Versatile and controllable access to functionalised carbocycles from unsaturated carbonyl compounds

Three different modes of hydroformylation/aldol reaction sequences involving either acid-catalysed aldol reactions, Mukaiyama aldol addition of pre-formed enolsilanes or aldol addition of in situ generated boron enolates can be applied to unsaturated ketones and ketoesters to afford the corresponding carbocyclic aldol adducts in good yields proceeding through the intermediate activated ketoaldehydes. In selected cases, complimentary, synthetically useful diastereoselectivities were observed in the products.

SUBSTITUTED TETRAHYDROBENZOPYRROLYL-FURANOIC ACID DERIVATIVES AS PHOSPHOLIPASE A2 INHIBITORS

Compounds of the formula wherein R is hydrogen, alkyl1-8, geminal alkyl1-3, un-substituted or substituted aryl; X is alkylene, ?CR1=CR2? (E and/or Z), carbonyl, oxygen or sulfur, wherein one of Ri and R2 is alkyli.3 and the other is hydrogen; Y is unsubstituted alkyh-n or substituted by one or more alkyl1-3 groups, or unsubstituted or substituted phenylalkyl 1-3; or a salt thereof with a pharmaceutically acceptable base, are described. The compound of formula I are potent inhibitors of phospholipase A2 (PLA2) and are therefore useful in the treatment of inflammatory diseases, such as, psoriasis, inflammatory bowel disease, asthma, allergy, arthritis, dermatitis, gout, pulmonary, myocardial ischemia and trauma induced inflammation, such as, spinal cord injury