Chemoenzymatic Synthesis of (+)-Asperpentyn and the Enantiomer of the Structure Assigned to Aspergillusol A.
Total syntheses of (+)-asperpentyn (1) and compound ent-2, the enantiomer of the structure, 2, assigned to the natural product aspergillusol A are reported. Both reaction sequences employ the enzymatically derived and enantiomerically pure cis-1,2-dihydrocatechol 4 as starting material and use Sonogashira cross-coupling chemistry to install the required enyne side-chain. The (1)H and (13)C NMR spectroscopic data derived from compound ent-2 match those reported for aspergillusol A, thus suggesting that the gross structure of this natural product has been assigned correctly, although its absolute stereochemistry remains unclear.
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Ping
P
Lan
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Lauren E
LE
White
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Ehab S
ES
Taher
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Prudence E
PE
Guest
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Martin G
MG
Banwell
Research School of Chemistry, Institute of Advanced Studies, The Australian National University , Canberra, ACT 2601, Australia.
Anthony C
AC
Willis
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D053138:Cyclohexenes / Q000138:chemical synthesis* / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D013237:Stereoisomerism; D014443:Tyrosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
D001688:Biological Products; D053138:Cyclohexenes; D004852:Epoxy Compounds; C545427:aspergillusol A; C538695:asperpentyn; D014443:Tyrosine