One-pot formation and derivatization of di- and triynes based on the Fritsch-Buttenberg-Wiechell rearrangement.
A divergent, one-pot synthesis of functionalized polyynes has been developed. Beginning with the appropriately substituted dibromoolefinic precursor, a carbenoid Fritsch-Buttenberg-Wiechell (FBW) rearrangement is used to generate the lithium acetylide of a conjugated polyyne framework, and subsequent trapping with carbon-based electrophiles provides for in situ formation of a wide range of di- and triynes. The lithium acetylide formed from the FBW reaction can also undergo transmetalation to provide the corresponding zinc, copper, tin, or platinum acetylides, leading to the divergent formation of symmetrical and unsymmetrical conjugated acetylenes, as well as ynones.
Luu
Thanh
T
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
Morisaki
Yasuhiro
Y
Cunningham
Nina
N
Tykwinski
Rik R
RR
D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D000480:Alkynes