A Chemoenzymatic Synthesis of Hept-6-ene-2,5-diol Stereomers: Application to Asymmetric Synthesis of Decarestrictine L, Pyrenophorol, and Stagonolide E

Abstract

The stereomers of hept-6-ene-2,5-diol derivatives were conceived as useful chiral intermediates and were synthesized starting from sulcatol using two lipase-catalyzed acylation reactions as the key steps. The versatility of the intermediates was demonstrated by converting them to the titled tetrahydropyran, macrolide, and macrodiolide compounds using standard synthetic protocols.

New antifouling macrodiolides from the deep-sea-derived fungus Trichobotrys effuse DFFSCS021

“…The 1 H and 13 C NMR spectral data of 3 showed great similarity to those of 2 (Table 1) 9), and C-9 (from d C 68.7 to d C 67.0). Extensive analysis of the 1 H NMR, 13 C NMR, HSQC, HMBC, and 1 H-1 H COSY spectra of 3 inferred that 3 had the same planar structure as 2.…”

“…7 These simple macrodiolides possess promising biological activities and unique structures which make them attractive synthetic targets. [8][9][10] While natural 18-membered macrodiolide were few. 1,11 Previous study reported four novel aliphatic phenolic ethers from fungus Trichobotrys effuse.…”

Recent Advances in Lipase-Mediated Preparation of Pharmaceuticals and Their Intermediates

“…In this case, both key intermediates (3 S ,6 R )-acetate and (3 R ,6 S )-alcohol were obtained with high enantioselectivity ( E > 195), c 50%. The enantiomerically pure (3 R ,6 S )-alcohol was used as an intermediate in the synthesis of Stagonolide E. The chemoenzymatic synthesis of Pyrenophorol and Decarestrictine L involved the enantiomericaly pure allylic (3 S ,6 R )-acetate as key intermediate ( Scheme 32 ) [ 52 ].…”

“… Kinetic enzymatic acylation of rac -hept-6-ene-2,5-diol derivatives to produce key intermediates in the synthesis of the Stagonolide E, Pyrenophorol and Decarestrictine L [ 52 ]. …”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…[775]; (13) macrocyclic bis(lactone)s, including those employed in syntheses of C-glycosphingolipids [776], pyrenophorol (also includes cross metathesis employing an acrylate ester in an earlier step of the synthesis, plus a methyl vinyl ketone cross metathesis for synthesis of decarestrictine L and an acrolein cross metathesis for synthesis of a related lactone stagonolide E) [777], 4-ketoclonostachydiol (e.g. 309) [778]; (14) macrocyclic tris(lactone)s, including those employed for preparation of macrosphelide I [779], and a macrosphelide A-biotin chimera [780]; (15) macrocyclic keto-lactone for total synthesis of amphidinolide Y precursors [781]; (16) macyoclic lactone-furanophanes, including those employed for syntheses of the plumarellide ring system (e.g.…”