Palladium-catalyzed modular assembly of electron-rich alkenes, dienes, trienes, and enynes from (E)-1,2-dichlorovinyl phenyl ether.
We have devised a modular construction of electron-rich alkene derivatives from trichloroethylene (TCE). The three C-Cl bonds of TCE have sufficiently different reactivities that they can be sequentially and selectively functionalized. Following the substitution of one chlorine by phenol to generate (E)-1,2-dichlorovinyl ether, the C(1)-Cl group next participates in palladium-catalyzed cross-coupling reactions with a variety of organometallic reagents. Subsequently, the C(2)-Cl group can engage in cross-couplings, while the C(2)-H may be deprotonated and quenched with an electrophile. Thus, isomerically pure tri- and tetrasubstituted electron-rich alkenes may be accessed in as few as two steps from simple and inexpensive starting materials. This method is ideally suited for diversity-oriented synthesis of highly conjugated molecules of interest as chromophores or as potential molecular electronics. It also gives access to diverse building blocks for further synthetic elaboration into high-value compounds.
Geary
Laina M
LM
Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2.
Hultin
Philip G
PG
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004583:Electrons; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010647:Phenyl Ethers / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
C554640:(E)-1,2-dichlorovinyl phenyl ether; D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D010647:Phenyl Ethers; D014753:Vinyl Compounds; D010165:Palladium