Categories: C-C Bond Formation > Alcohols, Alkynes >
Synthesis of propargyl alcohols
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Recent Literature
Asymmetric alkynylation of aldehydes using catalytic amounts of
In(III)/BINOL enables a broad range of substrate generality with high
enantioselectivity due to the "bifunctional character" of the catalyst
activating both substrates.
R. Takita, K. Yakura, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc.,
2005,
127, 13760-13761.
Terminal alkynes undergo addition to aldehydes in up to 99% ee using truly
catalytic quantities of metal and ligand. The procedure is practical, facile,
and utilizes reactants that require no prior preparation; moreover, the Zn(II)
salt and both enantiomers of the chiral ligand are commercially available. The
conditions tolerate air and moisture and are very versatile.
N. K. Anand, E. M. Carreira, J. Am. Chem. Soc., 2001, 123, 9687-9688.
The use of N-methylephedrine as chiral additive enables a practical
synthesis of propargylic alcohols from terminal alkynes and aldehydes as readily
available starting materials. N-Methylephedrine can be purchased in
either enantiomeric form as an inexpensive commodity chemical.
D. E. Frantz, R. Fässler,
E. M. Carreira, J. Am. Chem. Soc., 2000, 122, 1806-1807.
Enantioselective additions of terminal acetylenes to aldehydes mediated by Zn(OTf)2
and (+)-N-methyl
ephedrine can be conducted in reagent grade toluene containing up to 1000 ppm H2O.
Products are isolated in high yield and high enantioselectivities.
D. Boyall, D. Frantz, E. M. Carreira, Org. Lett.,
2002, 4, 2605-2606.
In an asymmetric addition of lithium acetylides to carbonyl compounds in the
presence of a chiral lithium binaphtholate catalyst, slow addition of the
carbonyl compound improved the enantioselectivity. This reaction afforded
diverse chiral secondary and tertiary propargylic alcohols in high yields and
with good to high enantioselectivities.
S. Kotani, K. Kukita, K. Tanaka, T. Ichibakase, M. Nakajima, J. Org. Chem., 2014,
79, 4817-4825.
Schiff-base amino alcohols derived from L-phenylglycine are highly effective
ligands for the enantioselective addition of phenylacetylene to aromatic
ketones to give optically active tertiary propargylic alcohols.
C. Chen, L. Hong, Z.-Q. Xu, L. Liu, R. Wang, Org. Lett.,
2006,
8, 2277-2280.
A broad range of terminal alkynes add rapidly and efficiently to aldehydes via a
catalytically generated zinc acetylide in the presence of TMSOTf. In the absence
of TMSOTf, no reaction is observed.
C. W. Downey, B. D. Mahoney, V. R. Lipari, J. Org. Chem., 2009,
74, 2904-2906.
Tetrabutylammonium fluoride (TBAF) is a very efficient catalyst for a mild
and operationally simple addition of trialkylsilylalkynes to aldehydes, ketones,
and trifluoromethyl ketones in THF at room temperature. The reaction conditions
tolerate various aryl functional groups, such as chloro, trifluoromethyl, bromo,
and fluoro groups. Product yields are generally better than or comparable to
those in the literature.
V. R. Chintareddy, H. Wadhwa, J. G. Verkade, J. Org. Chem., 2011,
76, 4482-4488.
Commercially available 2 M Me2Zn in toluene is able to promote
the addition of phenylacetylene to aldehydes and ketones. This reactivity is
determined by a new mechanism, which is discussed. Broad scope, high
tolerance to functional groups, and a simple procedure make this new method
highly interesting.
P. G. Cozzi, J. Rudolph, C. Bolm, P.-O. Norrby, C. Tomasini, J. Org.
Chem., 2005,
70, 5733-5736.
A novel InBr3-Et3N reagent system promotes the alkynylation of
not only a variety of aromatic/heterocyclic or bulky aliphatic aldehydes but
also N,O- or N,S-acetals. The reaction of N-silyl-N,O-acetals
with
1-alkynes gives primary propargylic amines in
good yields.
N. Sakai, R. Kanada, M. Hirasawa, T. Konakahara, Tetrahedron, 2005,
61, 9298-9304.
Inexpensive BINOL in combination with Ti(OiPr)4 catalyzes
the reaction of alkynylzinc reagents with a broad range of aldehydes to
generate chiral propargyl alcohols with high enantioselectivity at room
temperature.
L. Liang, T. T.-L. Au-Yeung, A. S. C. Chan, Org. Lett., 2002,
4, 3799-3801.
A new method for the coupling of aldehydes or ketones with alkynyl
propiolates in the absence of a base was developed. The reagents involved in
this coupling reaction are easy to handle and tolerate various functional
groups.
S. P. Shani, K. Koide, Angew. Chem. Int. Ed., 2004, 43,
2525-2527.
A carbenoid Fritsch-Buttenberg-Wiechell (FBW) rearrangement of a substituted
dibromoolefinic precursor is used to generate a lithium acetylide, and
subsequent trapping with carbon-based electrophiles provides a wide range of di-
and triynes. The lithium acetylide formed from the FBW reaction can also undergo
transmetalation to provide zinc, copper, tin, or platinum acetylides.
T. Luu, Y. Morisaki, N. Cunningham, R. R. Tykwinski, J. Org. Chem., 2007,
72, 9622-9629.
