DIBAL-H, Diisobutylaluminium hydride
Recent Literature
The use of diethylaluminum benzenethiolate enables an efficient discrimination
between aldehydes and other carbonyl functions and allows a chemoselective in
situ reduction of ketones and methyl esters in the presence of aldehydes without
using traditional protecting group methodologies.
G. Bastug, S. Dierick, F. Lebreux, I. E. Markó, Org. Lett., 2012,
14, 1306-1309.
Treatment of 3-[(alkoxycarbonyl)alkyl]-substituted conjugated cycloalkenones
with diisobutylaluminum hydride at -78 °C followed by acid quenching
furnishes spiro ethers, whereas the corresponding 3-(carboxyalkyl)-substituted
cycloalkenones generate spiro lactones upon reaction with sodium borohydride
at 30 °C followed by acid quenching.
M.-C. P. Yeh, Y.-C. Lee, T.-C. Young,
Synthesis, 2006, 3621-3624.
A selective copper-catalyzed hydride addition to propargylic chlorides
enables a mild and efficient synthesis of allenes from propargylic chlorides in
the presence of diisobutylaluminum hydride. This transformation provides a wide
range of functionalized allenes in good to excellent yields with high regio- and
stereoselectivities.
Y. Kim, H. Lee, H. Lee, Org. Lett.,
2018, 20, 5478-5481.
Esters and Weinreb amides undergo reduction to the corresponding aldehydes
using DIBAL-H followed by same pot conversion to terminal alkynes utilizing the
Bestmann-Ohira reagent in good to excellent yields.
H. D Dickson, S. C. Smith, K. W. Hinkle, Tetrahedron Lett., 2004,
45, 5597-5599.
R. S. Porto, M. L. A. A. Vasconcellos, E. Ventura, F. Coelho, Synthesis, 2005, 2297-2306.
Vinylaluminum reagents prepared from the reaction of commercially available
DIBAL-H and a terminal alkyne can be used directly without purification in
catalytic asymmetric allylic alkylation reactions with allylic phosphates in the
presence of a readily available chiral N-heterocyclic carbene (NHC)
complex and a commercially available and air stable Cu salt.
Y. Lee, K. Akiyama, D. G. Gillingham, M. Kevin Brown, A. H. Hoveyda, J. Am. Chem. Soc., 2008,
130, 446-447.
Reliable, operationally simple, catalytic α-selective
hydroalumination reactions proceed in the presence of diisobutylaluminum
hydride and (Ni(dppp)Cl2), and, unlike
uncatalyzed transformations, generate little or no alkynylaluminum
byproducts. The derived α-vinyl halides and boronates can be synthesized
through direct treatment with the appropriate electrophiles.
F. Gao, A. H. Hoveyda, J. Am. Chem. Soc., 2010,
132, 10961-10963.
Many tertiary phosphine oxides undergo considerable reduction at ambient
temperature with diisobutylaluminum hydride and then stall due to inhibition.
Source of this inhibition is tetraisobutyldialuminoxane (TIBAO), which builds up
as the reaction proceeds and selectively coordinates the TPO starting material.
Several strategies have been found to circumvent this inhibition.
C. A. Busacca, R. Raju, N. Grinberg, N. Haddad, P. James-Jones, H. Lee, J. C.
Lorenz, A. Saha, C. H. Senanayake, J. Org. Chem., 2008,
73, 1524-1531.
Solvent-controlled hydroaluminations of Si-substituted alkynes with DIBAL-H
generate diastereomerically enriched alkenylaluminum reagents that
react with isocyanates at ambient temperature to afford
α-silyl-α,β-unsaturated amides in high yields. This method offers short reaction time, ease of purification, easily
accessible substrates, and gram-scale synthesis.
H. Lee, S. Cho, Y. Lee, B. Jung, J. Org. Chem., 2020, 85,
12024-12035.
An unprecedented hydroalumination of C=O bonds catalyzed by zirconocene
dichloride enables a site-selective deprotection of peracetylated functional
substrates. A mixed metal hydride, with 1:1 zirconium/aluminum stoichiometry, is
the reductive species.
T. Courant, M. Gavel, R. M. Q. Renard, V. Gandon, A. Y. P. Joosten, T.
Lecourt, J. Org. Chem., 2021, 86,
9280-9288.