Divergent synthesis of bioactive resorcinols isolated from the fruiting bodies of Hericium erinaceum: total syntheses of hericenones A, B, and I, hericenols B-D, and erinacerins A and B.
Total syntheses of 5'- and 7'-oxidized geranyl resorcylates isolated from the fruiting bodies of Hericium erinaceum and the submerged cultures of a Stereum species were achieved. Our synthesis features derivatization of a suitably functionalized 5'-oxidized geranyl phthalide as a common intermediate, which was obtained by Stille coupling between the phthalide core and the side chain, into a series of natural products by divergent functional group manipulations. The crucial C5'-oxygen functionality was installed at the initial stage by alkylation by an α-cyano ethoxyethyl ether. From a common synthetic intermediate, eight total syntheses including hericenones A, B, and I, hericenols B-D, and erinacerins A and B were achieved (hericenol B and erinacerin B were synthesized as racemates). The structure of hericenone B established in the isolation paper was unambiguously revised as the carbonyl regioisomer at the lactam moiety.
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
Shoji
S
Kobayashi
Hidetsugu
H
Tamanoi
Yuichi
Y
Hasegawa
Yusuke
Y
Segawa
Araki
A
Masuyama
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D007769:Lactams / Q000737:chemistry*; D015394:Molecular Structure; D010636:Phenols / Q000138:chemical synthesis* / Q000737:chemistry; D012118:Resorcinols / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry
D001688:Biological Products; D006574:Heterocyclic Compounds, 2-Ring; D006575:Heterocyclic Compounds, 3-Ring; D007211:Indoles; D007769:Lactams; D010636:Phenols; D012118:Resorcinols; D013729:Terpenes; C505044:erinacerin A; C505043:erinacerin B; C000594694:hericenol B; C000594695:hericenol C; C000594697:hericenol D; C557360:hericenone B; C535185:hericenone I