Stereocontrolled synthesis of acyclic 1,3-diols via condensation of tungsten-syn-pi-pentadienyl complexes with aldehydes. A new Prins reaction via s-trans-diene cationic intermediates.
In the presence of BF(3).Et(2)O, condensation of CpW(CO)(2)(syn-pi-2-methoxycarbonylpentadienyl) with aldehydes generated tungsten-eta(4)-trans-diene cation in cold toluene, and hydrolysis of this salt afforded tungsten-pi-allyl-anti-1,3-diols in good yields. This new synthesis of anti-1,3-diols represents an atypical Prins reaction that is applicable to normal aldehydes. The anti/syn ratios of 1,3-diols increased with an increase in the size of the aldehydes. These anti-1,3-diols were transformed into various complex oxygen heterocycles based on two demetalations: (1) conversion to an allyl cation followed by nucleophilic attack and (2) condensation with aldehydes via its CpW(NO)Cl derivative, to give functionalized alpha-methylene butyrolactones. A semi-emperical calculation was performed to deduce the transition-state structure to rationalize the anti-stereoselectivity.
Department of Chemistry, National Tsing-Hua University, Hsinchu, 30043, Taiwan, ROC.
Y L
YL
Lin
M H
MH
Cheng
W C
WC
Chen
S M
SM
Peng
S L
SL
Wang
H
H
Kuo
R S
RS
Liu