62788-60-7

Usage

Synthesis Reference(s)

Journal of the American Chemical Society, 102, p. 3642, 1980 DOI: 10.1021/ja00530a064Tetrahedron Letters, 18, p. 1245, 1977

Upstream product

• 5682-75-7 3-chloro-2-cyclohexenone 
• 2123-72-0 1,4-dilithiobutane 
• 62788-57-2 tricyclo<5.3.0.0^1,6>decan-5-one 
• 66227-93-8 6,7-epoxy-6-(trimethylsilyl)spiro<4.5>decane 
• 66227-87-0 6-(trimethylsilyl)spiro<4.5>dec-6-ene 
• 13388-94-8 spiro[4.5]decan-6-one 
• 63438-16-4 spiro[4.5]dec-6-en-6-yl trifluoromethanesulfonate 
• 16133-79-2 7-spiro[4.5]decanol 
• 1258979-35-9 9-isobutyloxyspiro[4.5]dec-8-en-7-one 
• 66227-81-4 spiro<4.5>decan-6-one benzenesulfonylhydrazone 
• 62788-61-8 7-chlorospiro<5.4>decan-3-one 
• 74056-08-9 3-(4-Bromobutyl)-2-cyclohexen-1-one 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 73872-64-7 cis-6-(trimethylsilyl)spiro<4.5>decan-7-ol 

Relevant academic research and scientific papers

Carbonyl 1,2-transposition through triflate-mediated a-amination

To date, it remains challenging to selectively migrate a carbonyl oxygen within a given molecular scaffold, especially to an adjacent carbon. In this work, we describe a simple one- or two-pot protocol that transposes a ketone to the vicinal carbon. This approach first converts the ketone to the corresponding alkenyl triflate, which can then undergo the palladium- and norbornene-catalyzed regioselective a-amination and ipso-hydrogenation enabled by a bifunctional hydrogen and nitrogen donor. The resulting "transposed enamine" intermediate can subsequently be hydrolyzed to produce the 1,2-carbonyl-migrated product. This method allows rapid access to unusual bioactive analogs through late-stage functionalization.

Acid-labile ester monomer having spirocyclic structure, polymer, resist composition, and patterning process

An acid-labile ester monomer of spirocyclic structure has formula (1) wherein Z is a monovalent group having a polymerizable double bond, X is a divalent group which forms a cyclopentane, cyclohexane or norbornane ring, R2 is H or monovalent hydrocarbon, R3 and R4 are H or monovalent hydrocarbon, or R3 and R4, taken together, stand for a divalent group which forms a cyclopentane or cyclohexane ring, and n is 1 or 2. A polymer obtained from the acid-labile ester monomer has so high reactivity in acid-catalyzed elimination reaction that the polymer may be used to formulate a resist composition having high resolution.

ACID-LABILE ESTER MONOMER HAVING SPIROCYCLIC STRUCTURE, POLYMER, RESIST COMPOSITION, AND PATTERNING PROCESS

An acid-labile ester monomer of spirocyclic structure has formula (1) wherein Z is a monovalent group having a polymerizable double bond, X is a divalent group which forms a cyclopentane, cyclohexane or norbornane ring, R2 is H or monovalent hydrocarbon, R3 and R4 are H or monovalent hydrocarbon, or R3 and R4, taken together, stand for a divalent group which forms a cyclopentane or cyclohexane ring, and n is 1 or 2. A polymer obtained from the acid-labile ester monomer has so high reactivity in acid-catalyzed elimination reaction that the polymer may be used to formulate a resist composition having high resolution.

Organobis(cuprates): A New Class of Reagents and Method for Spiroannelation

A one-step spiroannelation method applicable to the synthesis of the commonly encountered spirocyclic systems is described.The method involves the reaction of 3-halocycloalk-2-enones with a new type of cuprate reagent prepared from organodilithium reagents and copper thiophenoxide and is shown to provide efficient access to mspirononanes, spirodecanes, and spiroundecanes.The effects of temperature, concentration, and halogen variations on the efficiency of this process are reported for the reactions of 3-halo-5,5-dimethylcyclohex-2-enones 2a-c with 1,4-bis(CuSPhLi)butane (3).Under optimal conditions, chloroenone 2a reacts with reagent 3 to provide 9,9-dimethylspirodecan-7-one (5) in 96percent yield.The optimized conditions are found to apply generally to variously substituted halocyclopentenones and halocyclohexenones, providing the corresponding spirocyclic products in 76-93percent yield.The preparation of new dilithium reagents is also described along with their use in the spiroannelation procedure.The stability of the organobis(cuprates) is found to be influenced by the hybridization of the metal-bearing centers, with alkyl reagents more stable than alkenyl reagents.

Tricyclo1,6>decan-5-one and Tricyclo1,6>undecan-5-one. Synthesis and Selective Transformation to Spiro and Fused Bicyclic Systems

The title compounds (10 and 11) were prepared by copper-catalyzed intramolecular cycloaddition of cyclopentenyl (8) and cyclohexenyl (9) diazo ketones.Reduction of 10 and 11 with lithium in ammonia gave spiro compounds 12 and 14 while exposure to HCl gave

Silanes in Organic Synthesis. 9. Enesilylation as a Method for 1,2-Carbonyl Migration within Ketones and for Conversion to 1,2-Transposed Allylic Alcohols

Vinylsilanes are shown to be valuable synthetic intermediates in useful transformations of ketones.The epoxidation of vinylsilanes followed by lithium aluminium hydride reduction and oxidation with chromic acid and sulfuric acid in a two-phase (ether/water) system often gives high yields of 1,2-transposed ketones.With singlet oxygen and sequential sodium borohydride reduction, 2-trimethylsilyl alcohols are produced in which the α position of the parent ketone has been regiospecifically oxygenated.Fluoride ion promoted desilylation completes the conversion to the migrated allylic alcohol.