214599-33-4

Upstream product

• 79-01-6 Trichloroethylene 
• 188017-81-4 (2R)-10-(phenylthio)isoborneol 
• 214599-31-2 (1S,4R)-1-phenylsulfanylmethyl-7,7-dimethyl-bicyclo[2.2.1]heptan-2-one 
• 108-98-5 thiophenol 
• 78622-29-4 (1S,4R)-1-(iodomethyl)-7,7-dimethylbicyclo-[2.2.1]heptan-2-one 

Relevant academic research and scientific papers

Camphor-derived, chelating auxiliaries for the highly diastereoselective intermolecular Pauson-Khand reaction: Experimental and computational studies

A family of enantiomerically pure (2R)-10-(alkylthio)isoborneols [methylthio (1), neopentylthio (2), phenylthio (3)], specifically designed as chiral auxiliaries suitable for chirality transfer to cobalt in Pauson-Khand reactions, has been synthesized. The dicobalt hexacarbonyl complexes of the alkoxyacetylenes derived from these alcohols (10a-12a) can be converted to the rather stable, internally chelated, pentacarbonyl complexes lOb-12b by treatment with NMO. The intermolecular Pauson-Khand reactions of 10b-12b with strained olefins take place with synthetically useful rates at low temperatures (down to -20 °C), with high yields and diastereoselectivities: norbornene (77%; 92:8), norbornadiene (82%; 96:4), bicyclo[3.2.0]hept-6-ene (91%; 93:7). The major diastereomer of the adduct of lOb with norbornadiene, 14, has been used as the starting point for a synthesis of (S)-(-)-4-alkyl-2-cyclopentenones through a se'quence consisting of completely diastereoselective conjugate addition, reductive cleavage with recovery (>95%) of the chiral auxiliary, and retro Diels-Alder reaction. The stereochemical course of the reaction of 10b with norbornadiene has been analyzed and rationalized by theoretical means by using a combined semiempirical [PM3-(tm)/density functional theory [VWN-Perdew-Wang 91] approach.