A new reaction motif: "homo-S(N)2'-like" direct nucleophilic addition to neutral eta(3)-allylmolybdenum complexes. total synthesis of the antimalarial (+)-isofebrifugine.
Charge neutral TpMo(CO)(2)(5-acyloxy-eta(3)-pyranyl) and TpMo(CO)(2)(5-acyloxy-eta(3)-pyridinyl) scaffolds undergo a novel intermolecular "homo-S(N)2'-like" reaction with a variety of carbon nucleophiles. Combined with an annulative demetalation, the homo-S(N)2'-like substitution/annulative demetalation sequence rapidly generates 2,7-dioxabicyclo[4.3.0]nonane and 2-aza-7-oxabicyclo[4.3.0]nonane frameworks in good to excellent yields with high enantiopurity. An enantiocontrolled total synthesis of the antimalarial alkaloid (+)-isofebrifugine was achieved utilizing this reaction cascade.
Chen
Wenyong
W
Sanford S. Atwood Chemistry Center, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
Liebeskind
Lanny S
LS
D000962:Antimalarials / Q000138:chemical synthesis* / Q000737:chemistry*; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D011799:Quinazolines / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D000962:Antimalarials; D009942:Organometallic Compounds; D010880:Piperidines; D011725:Pyridines; D011799:Quinazolines; D008982:Molybdenum; C001207:febrifugine; C023666:pyridine
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