jo300631d_si_004.cif (42.63 kB)
Carbonylation of 1-Lithiobutadiene with Carbon Monoxide Followed by Intramolecular Acyllithiation of CC Double Bond and Intermolecular Acylation with Acid Chloride: Scope, Applications, and Mechanistic Aspects
dataset
posted on 2012-05-18, 00:00 authored by Heng Li, Lantao Liu, Fei Zhao, Congyang Wang, Chao Wang, Qiuling Song, Wen-Xiong Zhang, Zhenfeng XiThe carbonylation of a 1-lithio-1,3-butadiene derivative
with CO
gave rise to a butadienyl acyllithio intermediate, which underwent
an immediate intramolecular acyllithiation of the CC double bond, affording a lithio cyclopentadienyl enolate. The X-ray
structural analysis of the enolate revealed a dimer connected with
a “Li2O2” four-membered ring.
Subsequent intermolecular acylation of this enolate with acid chlorides
afforded β-keto-3-cyclopentenones, γ-keto-2-cyclopentenones,
or cyclopentadienyl ester derivatives. The stereo- and regioselectivity
of the in situ generated lithio cyclopentadienyl enolate with various
acid chlorides was investigated and analyzed, showing that the formation
of the above products was significantly dependent on both the substituents
on the butadienyl skeleton and the bulkiness of acid chlorides.