Thioether continued synthesis

Synthesis and structural characterization of synthetic analogs of liver alcohol dehydrogenase (LADH) continued to be one of the most investigated fields of research. A number of ligands suitable for modeling LADH have been reported and their hydroxo zinc complexes also described.133-135 [Zn(TmMes)(HOMe)]+, for example, exhibits a coordination environment that resembles aspects of that in LADH.136 The ethanol complex [Zn(Tm Bu)(HOEt)]+ has been also isolated.137 [NS2] donor ligands, that feature thioether donors, also provide coordination environments that mimic the active site of LADH.138,139... 

The reactions of lithiophosphide reagents with alkyl halides or sulphonate esters have continued to find wide application in the synthesis of new phosphines. A series of phosphino-ethers, e.g., (22), has been prepared from the reactions of chloromethyl-substituted ethers with lithium diphenylphosphide. " A one-step synthesis of macrocyclic phosphino-ethers and -thioethers (23) is afforded by the reactions of dilithio-organophosphides with bis(j8-chloroethyl)-ethers and -thioethers derived from ethane-1,2-diol and ethane-1,2-dithiol, respectively. " A new family of water soluble phosphonio-phosphine ligands (24) has been prepared by the reaction of a,o)-dihaloalkanes with one mole of lithium diphenylphosphide, followed by quatemisation of the intermediate w-haloalkylphosphine with trimethylphosphine. The new ligand system (25) has been prepared by the reaction of chloromethylbenzene-chromium tricarbonyl with... 

Ethereal LiAlH4-soln, added to an ice-cooled soln. of AICI3 in Na-dried ether, stirred 0.5 hr., then a soln. of l-oxa-4-thiaspiro[4.5]decane in ether added slowly with cooling, and stirring continued for 2 hrs. 2-(cyclohexylthio)-ethanol. Y 91.1%.—This reduction constitutes a convenient method for the synthesis of thioethers from 0x0 compounds. F. e., also hydroxyethers from cyclic acetals and ketals, s. E. L. Eliel and V. G. Badding, Am. Soc. 81, 6087 (1959). 

---