Categories: C-O Bond Formation >
Synthesis of acylals
Recent Literature
HBF4-SiO2 is an outstanding catalyst for a convenient,
chemoselective, and high-yielding protection of carbonyl compounds as acylals
under entirely solvent-free conditions.
V. T. Kamble, B. P. Bandgar, N. S. Joshi, V. S. Jamode, Synlett, 2006,
2719-2722.
Aldehyde 1,1-diacetates are efficiently formed in excellent yields from
aldehydes and acetic anhydride under solvent-free conditions at room temperature
in the presence of a catalytic amount of copper(II) tetrafluoroborate hydrate.
A. K. Chakraborti, R. Thilagavathi, R. Kumar, Synthesis, 2004,
831-833.
Geminal diacetates and dipivalates were prepared in high yields through
a mild and efficient reaction of aldehydes with acetic anhydride or pivalic
anhydride using zirconium (IV) chloride as a catalyst under solvent free
conditions. Regeneration of aldehydes from the acylals was achieved using
the same catalyst in methanol.
G. Smitha, Ch. S. Reddy, Tetrahedron, 2003, 59,
9571-9576.
Various alcohols, phenols, amines and thiols
may easily be converted into acetate derivatives by treatment
with acetic anhydride in the presence of
acetonyltriphenylphosphonium bromide in good yields at room
temperature. With the same precatalyst, both aliphatic and aromatic aldehydes
can be transformed into the corresponding gem-diacetates under reflux
conditions.
A. T. Khan, L. H. Choudry, S. Ghosh, Eur. J. Org. Chem., 2005,
2782-2787.
In the presence of TBAI/TBHP, treatment of esters possessing a methylene carbon
α-to oxygen with benzylamines provides bis-esters rather than the expected
amides. Under these oxidative conditions, benzylamines generate less
nucleophilic carboxylates, which couple at sp3 C-H bonds of esters
and cyclic ethers to yield bis-acyl ketals and α-acyloxy ethers, respectively.
G. Majji, S. Rajamanickam, N. Khatun, S. K. Santra, B. K. Patel, J. Org. Chem.,
2015,
80, 3440-3446.