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

Abstract

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 beta-ionone, (ii) includes a regiospecific oxidative functionalization of beta-ionone leading to 1-acetoxy-beta-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.

Structure-Activity Relationship Studies of Strigolactone-Related Molecules for Branching Inhibition in Garden Pea: Molecule Design for Shoot Branching

“…GR24, 29-epi-GR24, and derivatives 1, 29-epi-1, 2, 29-epi-2, 4, and 5 (Fig. 2) were prepared according to the procedures described Thuring et al, 1997;Reizelman et al, 2003); compound 3 was prepared according to the procedure described by Fell and Harbridge (1990) and d'orenone according to the procedure of Schachtschabel and Boland (2007). (+)-and (2)-Solanacol and solanacyl acetate were prepared by the procedure described previously in our laboratory (Chen et al, 2010).…”

Early and Late Trisporoids Differentially Regulate β-Carotene Production and Gene Transcript Levels in the Mucoralean Fungi Blakeslea trispora and Mucor mucedo

“…Therefore, preincubated (for 90 h) individual mating partners were treated with the stimulants at 14 g ml Ϫ1 per plate, incubated for an additional 44 h, and extracted to quantitatively analyze ␤-carotene production. All of those compounds enlisted, compounds 2, 7, 10, 11, 12, and 13, were synthesized in our laboratory (39). We presumed they are the probable trisporoid intermediates, based on our synthetic approach, as none of them had yet been isolated or reported as a natural product from any mucoralean members, suggesting their low abundance, instability, or quick biotransformations to sex hormones.…”

Easy Access to a Cyclic Key Intermediate for the Synthesis of Trisporic Acids and Related Compounds

“…Several routes to trisporoids such as trisporins, methyl trisporates, trisporols, and free trisporic acids have been developed and reported [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. The disadvantage of most routes is the large number of steps required for the synthesis of the final targets and the lack of flexibility to produce early and late trisporoids along the same protocol using common intermediates.…”

“…The disadvantage of most routes is the large number of steps required for the synthesis of the final targets and the lack of flexibility to produce early and late trisporoids along the same protocol using common intermediates. The approaches by Boland [31] and Rodríguez-García [32] are examples of modern strategies that carry out the synthesis of compounds of this family by using organometallic couplings. However, they lead only to early trisporoids without oxygen functions in the gem-dimethyl group of the cyclohexane.…”