Efficient Generation of a Trisporoid Library by Combination of Synthesis and Biotransformation

• Published in: Journal of organic chemistry Vol. 72; no. 4; pp. 1366 - 1372
• Main Authors: Schachtschabel, Doreen, Boland, Wilhelm
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 16.02.2007; Amer Chemical Soc
• Subjects: Alicyclic compounds, terpenoids, prostaglandins, steroids; Biotransformation; Chemistry; Chemistry, Organic; Exact sciences and technology; Fatty Acids, Unsaturated - chemical synthesis; Fatty Acids, Unsaturated - chemistry; Fatty Acids, Unsaturated - metabolism; Fungi - metabolism; Molecular Structure; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Terpenoids; B-METHYL-ESTER; OXIDATION; FACILE SYNTHESIS; PHEROMONE; MUCOR-MUCEDO; STEREOCHEMISTRY; BLAKESLEA-TRISPORA; SEXUAL HORMONES; VITAMIN-A; ACID-B; Deuterium; Terpenoid; Molecular flexibility; Phycomycetes; Pheromone; Biosynthesis; Regiospecificity; Fungi; Functionalization; Biotransformation; Chemical compound library; Monoterpene; Oxidation; Chemical synthesis; Labelled compound; Thallophyta; Blakeslea trispora
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo062236c

Trisporic acids and their biosynthetic precursors represent a family of powerful fungal pheromones and morphogenetic factors. A highly flexible synthetic protocol is described that (i) provides rapid access to nonfunctionalized early trisporoids from β-ionone, (ii) includes a regiospecific oxidative functionalization of β-ionone leading to 1-acetoxy-β-ionone giving access to functionalized trisporoids, and (iii) utilizes a biotransformation of early synthetic trisporoids by growing cells of Blakeslea trispora to prepare late trisporoids including trisporic acids. The same protocol also provides deuterium-labeled trisporoids such as trisporin B [2H3]-19. Administration of [2H3]-19 to growing cells of the (−)-mating type of B. trispora resulted in the formation of the labeled trisporols [2H3]-20 and [2H3]-21. Growing cultures containing both mating types can be used to prepare trisporic acids from early precursors.