Categories: C-N Bond Formation > Synthesis of azides >
Synthesis of β-azidoketones, β-azidoacids and related compounds
Recent Literature
A chiral (salen)Al complex catalyzes the highly enantioselective conjugate
addition of carbon- and nitrogen-based nucleophiles to various acyclic α,β-unsaturated
ketones providing access to a wide range of useful chiral building blocks in
high yield and enantiomeric excess.
M. S. Taylor, D. N. Zalatan, A. M. Lerchner, E. N. Jacobsen, J. Am. Chem. Soc.,
2005,
127, 1313-1317.
Tertiary amines catalyze a β-azidation of α,β-unsaturated carbonyl compounds
with a 1:1 mixture of TMSN3 and AcOH as azide source. Tertiary
amines, either in solution or bound to a solid support, can be used.
D. J. Guerin, T. E. Horstmann, S. J. Miller,
Org. Lett., 1999, 1, 1107-1109.
Amberlite IRA900N3 is an excellent and recyclable organocatalyst
for the azidation of α,β-unsaturated ketones with trimethylsilyl azide under
solvent-free conditions. This procedure is a green tool for the preparation
of β-azido ketones under mild conditions with good yields.
L. Castrica, F. Fringuelli, L. Gregoli, F. Pizzo, L. Vaccaro, J. Org. Chem., 2006,
71, 9536-9539.
An iron-catalyzed acyl-azidation of alkenes provides unsymmetrical β-azido
ketones
under mild reaction conditions from aromatic aldehydes or aliphatic aldehydes as
the acyl radical precursors, TMSN3 as the azido source, and TBHP as
the initiator. The synthesized unsymmetrical β-azido ketones can be easily
transformed into valuable functionalized compounds.
L. Ge, Y. Li, H. Bao, Org. Lett.,
2019, 21, 256-260.
A mild oxidation of selected anions (N3-, SCN-, I-, and Br-) by ceric ammonium
nitrate (CAN) in the presence of substituted cyclopropyl alcohols provides β-functionalized
ketones in short reaction times. This method provides an alternative
pathway to important starting materials and intermediates in organic synthesis.
J. Jiao, L. X. Nguyen, D. R. Patterson, R. A. Flowers II, Org. Lett., 2007,
9, 1323-1326.
Chiral N,N'-dioxide/Fe(OTf)2 complexes catalyze an
unprecedented highly diastereo- and enantioselective bromoazidation of
α,β-unsaturated ketones. An array of aryl, heteroaryl, and alkyl substituted
α,β-unsaturated ketones were transformed to the corresponding α-bromo-β-azido
ketones in high yields with excellent diastereo- and enantioselectivities. The
catalytic system was also applicable for chloroazidations and iodoazidations.
P. Zhou, L. Lin, L. Chen, X. Zhong, X. Liu, X. Feng, J. Am. Chem. Soc., 2017,
139, 13414-13419.
A chiral
iron(II) complex catalyzes a regio- and enantioselective α-halo-β-azido difunctionalization of both
α,β-unsaturated amides and α,β-unsaturated esters under mild reaction conditions
to provide a broad spectrum of valuable functionalized amides and esters.
P. Zhou, X. Liu, W. Wu, C. Xu, X. Feng, Org. Lett., 2019, 21,
1170-1175.