Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of β-Cyanohydrins
| Related: |
 |
 |
Recent Literature
Cooperative catalysis of a cationic Ru complex, DBU, and NaPF6 enabled
activation of acetonitrile as a nucleophile under mild basic conditions. The
nucleophilic 1,2-addition of in situ-generated, Ru-bound, metalated nitrile to
aldehydes and imines proceeded smoothly.
N. Kumagai, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc.,
2004,
126, 13632-13633.
α-Alkylated (dimethylsilyl)acetonitriles react spontaneously with aldehydes in
DMSO to give β-hydroxynitriles in very good yields. The addition to ketones is
effectively promoted by using MgCl2 or CaCl2. (Dimethylsilyl)acetonitrile,
which shows lower reactivity, adds efficiently to aldehydes and ketones under
catalysis by AcOLi or MgCl2.
T. Jinzaki, M. Arakawa, H. Kinoshita, J. Ichikawa, K. Miura, Org. Lett., 2013,
15, 3750-3753.
In the presence of SiCl4 and a catalytic amount of a chiral
phosphoramide, silyl ketene imines undergo extremely rapid and high yielding
addition to a wide variety of aromatic aldehydes with excellent diastereo- and
enantioselectivity. The nitrile function serves as a useful precursor for
further synthetic manipulation.
S. E. Denmark, T. W. Wilson, M. T. Burk, J. R. Heemstra, Jr., J. Am. Chem. Soc., 2007,
129, 14864-14865.
Related
A catalytic DKR-ATH process for the enantio- and diastereoselective reduction
of α-substituted-β-keto carbonitriles enables the simultaneous construction of
β-hydroxy carbonitrile scaffolds with two contiguous stereogenic centers in high
yields and excellent enantio- and diastereoselectivities.
F. Wang, T. Yang, T. Wu, L.-S. Zheng, C. Yin, Y. Shi, X.-Y. Ye, G.-Q. Chen, X.
Zhang, J. Am. Chem. Soc.,
2021, 143, 2477-2483.
An iridium-catalyzed, chemoselective, asymmetric transfer hydrogenation of α-substituted
acetophenones using formic acid as reductant can be performed in water and open
to air.
O. Soltani, M. A. Ariger, H. Vázquez-Villa, E. M. Carreira, Org. Lett., 2010,
12, 2893-2895.
(R)-β-Hydroxy nitriles were obtained via a reduction catalyzed by a
recombinant carbonyl reductase with excellent optical purity and were further
converted to (R)-β-hydroxy carboxylic acids via a nitrilase-catalyzed
hydrolysis. The present study allows ready access to both chiral β-hydroxy
nitriles and β-hydroxy carboxylic acids of pharmaceutical importance.
D. Zhu, H. Ankati, C. Mukherjee, Y. Yang, E. R. Biehl, L. Hua, Org. Lett., 2007,
9, 2561-2563.