A highly regio- and stereoselective formation of bicyclo[4.2.0]oct-5-ene derivatives through thermal intramolecular [2 + 2] cycloaddition of allenes.
Thermal [2 + 2] cycloaddition of allenes with an additional multiple bond is described. By simply heating the allenenes or allenynes having a three-atom tether in an appropriate solvent such as dioxane or DMF, the distal double bond of the allenic moiety regioselectively participates in the cycloaddition to form bicyclo[4.2.0]oct-5-ene derivatives in good to excellent yields. In all the reactions of allenenes, the olefin geometry was completely transferred to the cycloadducts. While the reaction of terminal allenes afforded bicyclic cyclobutane derivatives as a single isomer, the cycloaddition of some internal allenes with axial chirality yielded a diastereomeric mixture of cycloadducts. These results are in good accordance with the stepwise mechanism through a biradical intermediate with a coplanar allyl radical.
Ohno
Hiroaki
H
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. hohno@pharm.kyoto-u.ac.jp
Mizutani
Tsuyoshi
T
Kadoh
Yoichi
Y
Aso
Akimasa
A
Miyamura
Kumiko
K
Fujii
Nobutaka
N
Tanaka
Tetsuaki
T
D000466:Alkadienes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D003500:Cyclization; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
D000466:Alkadienes; D000480:Alkynes; D001643:Bridged Bicyclo Compounds; C025947:propadiene; D010165:Palladium