Abstract
Carbenoid, a complex of metal and carbene, undergoes various reactions such as C-H insertion, cyclopropanation, and ylid formation reactions with a range of substrates. Stereo- and chemoselectivity of these reactions is well known to depend upon the nature of the central metal ion and its bystander ligand. Thus, we synthesized new type of optically active metal complexes : bipyridine-copper (I) complex, (salen) cobalt (III) complex, and zinc-1, 1' -bi-2, 2' -naphthol-3, 3' -dicarboxamide complex and used them as catalysts for carbenoid-mediated asymmetric reactions. With these chiral metal complexes, we could achieve i) the first highly enantiospecific ring expansion reaction of oxetane to tetrahydrofurans, ii) highly enantio- and trans-selective cyclopropanation, iii) highly enantioselective Simmons-Smith reaction, and iv) highly stereoselective catalytic [2, 3] Wittig rearrangement. This study greatly expanded the scope of asymmetric carbenoid reactions.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
