| The asymmetric synthesis of chiral amines is an important goal of modern organic chemistry because amines are found in a large percentage of biologically active compounds. tert-Butanesulfinamide is increasingly being used in both academics and industry as a convenient chiral ammonia equivalent. However, with the increasing use of tert-butanesulfinamide for the asymmetric synthesis of amines, the scale limitations of the original synthesis of this chiral ammonia equivalent became apparent. In this thesis, a superior, completely scalable catalytic enantioselective method for the synthesis of tert-butanesulfinamide is presented that has allowed for its preparation on multikilogram scale. Improvements include complete scale independence, a more readily available catalyst, a switch to a more benign solvent, complete scavenging of the thiol byproduct that is generated, and elimination of all purification steps save recrystallization of the final product.; In the second part, a rhodium-catalyzed asymmetric synthesis of branched amines is presented that allows for the highly stereoselective synthesis of aryl-aryl and aryl-alkyl amines from readily available, highly-functionalized arylboronic acids and tert-butanesulfinyl, diphenylphosphinoyl, or Boc amines. The reactions are often high yielding and do not require low temperatures for high selectivities. Preliminary results extending this method to the asymmetric synthesis of phenylglycines is also presented. |
