Conversion of 1-alkenes into 1,4-diols through an auxiliary-mediated formal homoallylic C-H oxidation.
The ubiquitous nature of C-H bonds in organic molecules makes them attractive as a target for rapid complexity generation, but brings with it the problem of achieving selective reactions. In developing new methodologies for C-H functionalization, alkenes are an attractive starting material because of their abundance and low cost. Here we describe the conversion of 1-alkenes into 1,4-diols. The method involves the installation of a new Si,N-type chelating auxiliary group on the alkene followed by iridium-catalysed C-H silylation of an unactivated δ-C(sp(3))-H bond to produce a silolane intermediate. Oxidation of the C-Si bonds affords a 1,4-diol. The method is demonstrated to have broad scope and good functional group compatibility by application to the selective 1,4-oxygenation of several natural products and derivatives.
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St, Room 4500, Chicago, Illinois 60607, USA.
Nugzar
N
Ghavtadze
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St, Room 4500, Chicago, Illinois 60607, USA.
Ferdinand S
FS
Melkonyan
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St, Room 4500, Chicago, Illinois 60607, USA.
Anton V
AV
Gulevich
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St, Room 4500, Chicago, Illinois 60607, USA.
Chunhui
C
Huang
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St, Room 4500, Chicago, Illinois 60607, USA.
Vladimir
V
Gevorgyan
D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry; D007495:Iridium / Q000737:chemistry; D010084:Oxidation-Reduction; D011789:Quantum Theory; D012821:Silanes / Q000737:chemistry
D000438:Alcohols; D000475:Alkenes; D001688:Biological Products; D012821:Silanes; D007495:Iridium; D002244:Carbon; D006859:Hydrogen