Perylenequinone natural products: total synthesis of hypocrellin A.
An efficient and stereoselective total synthesis of the perylenequinone natural product hypocrellin A (1) is described. The key features include a potentially biomimetic 1,8-diketone aldol cyclization to set the centrochiral C7,C7'-stereochemistry, bis(trifluoroacetoxy)iodobenzene mediated oxygenation, a palladium-catalyzed decarboxylation, and an enantioselective catalytic oxidative 2-naphthol coupling to establish the biaryl axial chirality. The helical stereochemistry is formed from an axial chiral intermediate and is then utilized in a dynamic stereochemical transfer to dictate the stereochemistry of the C7,C7'-seven membered ring formed during the aldol cyclization.
O'Brien
Erin M
EM
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Morgan
Barbara J
BJ
Mulrooney
Carol A
CA
Carroll
Patrick J
PJ
Kozlowski
Marisa C
MC
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D019800:Phenol; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D001688:Biological Products; D011809:Quinones; D019800:Phenol; D010569:Perylene; C048388:hypocrellin A