Phenyl chlorothionocarbonate

Nikolai S. Zefirov Moscow State University, Moscow, Russia 

Physical Data bp 81-83 06 mmHg fp 81 °C t/1.248 gcm . Solubility sol chloroform, THF Form Supplied in colorless liquid. 

Handling, Storage, and Precautions corrosive moisture sensitive should be stored in airtight containers which exclude moisture incompatible with alcohol solvents. 

Synthetic intermediates can be selectively deoxygenated without reduction of other functional groups such as esters, ketones, and oxime ethers (eq 3), as well as epoxides, acetate esters, and alkenes.  

Radical Coupling and Cyclization Reactions. Phenyl thionocarbonate esters derived from alcohols serve as efficient precursors for the generation of radical intermediates which can be used for the formation of new carbon-carbon bonds. For example, a 4-thionocarbonate ester derived from L-lyxose undergoes a stereoselective allylation upon photolysis in toluene in the presence of 2.0 equiv of allyltributylstannane (eq 6). Photochemical initiation is preferable to chemical initiation using azobisisobu-tyronitrile which results in the formation of side products at the 

85% of 6-thionocarbonate. Further treatment with tributyltin hydride affords the corresponding deoxyglucose derivatives in high yield. 

Oxime ethers derived from hydroxy aldehydes, upon conversion to their phenyl thionocarbonate esters, undergo radical cy-clizations resulting in the formation of carbocycles. For example, an oxime ether obtained from o-glucose is converted into its phenyl thionocarbonate ester at C-5 and, upon heating in benzene in the presence of tributyltin hydride, affords cyclopentanes in 93% yield as a 62 38 mixture of two diastereomers (eq 7). In general, only low to modest stereoselectivity between the newly formed stereocenters is observed in a number of substrates examined. 

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Phenyl chlorothionocarbonate, C6HsOCC1 (1). Mol. wt. 218.11, b.p. 81-8376 mm. The reagent is prepared by reaction of phenol with thiophosgcnc in aqueous... 

ALCOHOLS Chlorotrimethylsilane-Sodium iodide. Iron carbonyl. Phenyl chlorothionocarbonate. Potassiurr>-18-Crown-6. Tri-n-bulyhin hydride. CARBONYL COMPOUNDS Bis(ben-zoyloxy)borane. Bis(triphenyIplios-pliine looppert I) te trahydrobora te. Cutecholborane. 

Phase-transfer catalysts, 220, 221,305-306 Phenanthrenes, 319, 320 9-Phenanthrol, 431 Phenol annelation, 272 Phenoxysulfonyl azide, 377-378 Phenylacetaldehyde, 217 Phenylacetylene, 7 2 (S)-3-Phenyl-1-butene, 36 Phenyl chlorothionocarbonate, 306-307 Phenyl cyanate, 307-308 Phenyldiazomethane, 308 o-Phenylene phosphorochloridate, 91-92 o-Phenylglydne methyl ester, 308 Phenyl isocyanate, 309 Phenyl isocyanide, 309-310 Phenyl iso thiocyanate, 122 Phenyllithium, 5... 

Related Reagents. Carbon Disulfide A(-Hydroxypyridine-2-thione l,l -Thiocarbonyldiimidazole p-Tolyl Chlorothionocar-bonate Phenyl Chlorothionocarbonate. 

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