Synthesis of Macrocyclic Lactams and Lactones Containing Sulfur and Nitrogen

Functionalisation of Macroheterocycles with Preserving and Changing Their Sizes

“…Cyclization leads to the formation of cycles (214) and precatenane (215) coupled to each other that turn into two isolated macrocycles (216) and catenane (207), respectively, when breaking auxiliary bonds (Scheme 45). [109] This was realised in synthesis of [2]catenane (217) when using Pd(II) directed cyclization of tridentate ligand (218) with monodentate macrocycle (219) (Scheme 46). [112] Similarly to catenanes, rotaxanes can be synthesized by both statistical and directed methods.…”

“…Consequently, alongside with the initial macrocycle (205), some amounts of rotaxane (221) and molecular barbells of (222) Macroheterocycles Functionalization Accompanied by Preservation and Changing Their Size Catalysed acylation with bulky acid anhydrides of pseudo-rotaxanes that have a hydroxyl group at the end of the axis is one of the most methods of synthesis of [2]rotaxanes comprising of crown ethers and secondary ammonium salts. Thus, a series of [2]rotaxanes (223a-d) were synthesized from dibenzo-24-crown-8 (224) and dibenzylammonium salts (225a-d) under catalysis by Bu 3 P (Scheme 48). [113][114][115] When a catalyst is a strong acid, e.g.…”

“…1,5,9-Triazacyclodecane (14) is an extremely basic azacrown compound (pK a 3 =12.3-12.7) used as an efficient extractant for gold dicyanate anion [Au(CN) 2 ] -. Good solubility of the resulting complex in water significantly worsens its transfer to the organic phase.…”

“…Thus, compounds with high antiproliferative activities and abilities to inhibit Hsp90-dependent protein degradation that are potential agents to cure cancer (Scheme 1) [4] are obtained in synthesis of radamicine (1a) and its seco analogues (1b-i) that represent series of macrocyclic chimeras radicicol (2) and geldanamycin (3) that are strong inhibitors of the Hsp90 N-terminal ATP-binding -macroamidation of acyclic precursors (4a-i) under the action of HATU and oxidation of the resulting hydroquinones (5a-i) into appropriate quinones (6c-i) (Scheme 1).…”

“…Reviews [1,2] describe in detail methods of development of macrocycles with ester, nitrogen-, and sulphur-containing functions, and also the use of these methods in streamlined synthesis of biologically active compounds was demonstrated on specific examples. This literature review presents methods for functionalisation of macroheterocycles themselves that proceed with both conservation and a change in their skeleton beginning with 1963 including 3 articles described in the review of 1999.…”