Polymer-supported thiobenzophenone: a self-indicating traceless 'catch and release' linker for the synthesis of isothiocyanates

Tetrahedron Letters

Volumn 48, Issue 31, 2007, Pages 5355-5358

  Burkett, Brendan A ^a   Kane Barber, Jacqueline M ^a   O'Reilly, Robert J ^a   Shi, Lei ^a  

^a VICTORIA UNIVERSITY OF WELLINGTON   (New Zealand)

Author keywords

Catch and release; Isothiocyanates; Polymer supported synthesis; Self indicating

Indexed keywords

BENZOPHENONE DERIVATIVE; ISOTHIOCYANIC ACID DERIVATIVE; LEWIS ACID; NITRILE OXIDE; POLYMER; THIAZOLE DERIVATIVE; THIOBENZOPHENONE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CYCLOADDITION; SYNTHESIS;

EID: 34347331170     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2007.06.025     Document Type: Article

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18. -1) was swelled in dry, degassed toluene (16 mL/g of resin) under an inert atmosphere for 10 min and the resulting suspension was heated at reflux. Lawesson's reagent (1.5 equiv) was added in one portion and the polymer beads turned blue within 5 min. Heating was continued for a further 5 h after which time 10 mL of acetone was added to the mixture. The resulting mixture was allowed to react for a further hour before filtering the hot reaction mixture. The resulting polymer-supported thione was filtered and washed with dichloromethane (5 × 40 mL/g of polymer). The blue thiobenzophenone polymer-support 1 was then dried in vacuo and used immediately in the next step.
19. -1) in dichloromethane (20 mL/g) was added the appropriate hydroximoyl chloride (1.1 equiv). The resulting mixture was shaken gently under an inert atmosphere for 5 min followed by the addition of triethylamine (1.1 equiv) dropwise over a period of a few minutes. The reaction was allowed to proceed for 2 h. Complete cycloaddition was evident from the complete disappearance of the blue colour from the polymer beads. The polymer support was then filtered and washed with boiling toluene (2 × 40 mL/g), acetone (2 × 40 mL/g), diethyl ether (2 × 40 mL/g) and dichloromethane (2 × 100 mL/g). The resulting beads were then dried in vacuo and stored under nitrogen.
20. -1) of zinc chloride (anhydrous) was added. The reaction was allowed to proceed under reflux for 24 h and the polymer was filtered and washed with dichloromethane (2 × 10 mL/g). The washings were collected and the solvent was removed under reduced pressure. In all cases the resulting isothiocyanates were isolated in good yield and were of high purity.