Categories: C-C Bond Formation > Chains >
Propargylic Substitution
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Recent Literature
A general and efficient FeCl3-catalyzed substitution reaction of
propargylic alcohols with carbon- and heteroatom-centered nucleophiles such
as allyl trimethylsilane, alcohols, aromatic compounds, thiols, and amides,
forms new C-C, C-O, C-S and C-N bonds.
Z.-P. Zhan, J.-L. Yu, Y.-Y. Cui, R.-F. Yang, W.-Z. Yang, J.-P. Li, J. Org. Chem., 2006,
71, 8298-8301.
LaCl3·2LiCl catalyzes a propargylation of Grignard reagents in the
absence of ligand in high regioselectivity and stereospecificity. The approach
shows a wide substrate scope using alkyl or (hetero)aryl Grignard reagents and
alkynyl electrophiles with different leaving groups. This protocol was further
applied for the formal synthesis of frondosin B.
D. Sun, T. Rajeshkumar, Y. Li, J. Xu, R. Chen, Z. Wan, Z. Lv, L. Maron, Y.-H.
Chen, Org. Lett., 2023, 25,
6730-6735.
A general and efficient FeCl3-catalyzed substitution reaction of
propargylic alcohols with carbon- and heteroatom-centered nucleophiles such
as allyl trimethylsilane, alcohols, aromatic compounds, thiols, and amides,
forms new C-C, C-O, C-S and C-N bonds.
Z.-P. Zhan, J.-L. Yu, Y.-Y. Cui, R.-F. Yang, W.-Z. Yang, J.-P. Li, J. Org. Chem., 2006,
71, 8298-8301.
A palladium-catalyzed cross-coupling of allyl boronates and chiral propargyl
acetates
delivers chiral 1,5-enynes with excellent levels of chirality transfer. The
reaction can be applied across a broad range of substrates.
M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc., 2012,
134, 8770-8773.
The reaction of alkoxides with boron trichloride results in the generation
of cations that can be allylated in subsequent transformations. The absence
of Brønsted acids can make a significant difference in such syntheses.
G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006,
128, 11320-11321.
An efficient Cu(OTf)2-catalyzed sp3-sp2
coupling of propargylic alcohols with terminal alkenes gives a diverse range of
1,4-enynes in very good yields. The reaction is tolerant to air and
atom-economical.
G.-B. Huang, X. Wang, Y.-M. Pan, H.-S. Wang, G.-Y. Yao, Y. Zhang, J. Org. Chem., 2013,
78, 2742-2745.
An iridium-catalyzed stereoselective coupling of allylic ethers and alkynes
provides 3,4-substituted 1,5-enynes with excellent regio-, diastereo-, and
enantioselectivities, and the protocol is functional group tolerant. Moreover,
conditions are reported that allow the reaction to proceed with complete
reversal of diastereoselectivity.
J. Zhu, Y. Wang, A. D. Charlack, Y.-M. Wang, J. Am. Chem. Soc.,
2022, 144, 15480-15487.
Under different conditions, the reaction of propargyl alcohols and terminal
alkynes leads to the selective formation of 1,4-diynes and polysubstituted
furans/pyrroles. Water is the only byproduct in the atom economic, selective
synthesis of 1,4-diynes and pyrroles, whereas the synthesis of furans is fully
atom economic.
T. Wang, X.-l. Chen, L. Chen, Z.-p. Zhan, Org. Lett., 2011,
13, 3324-3327.
C-O bond cleavage of lithium alkoxides occurs readily at room temperature in the
presence of titanium(IV) halides. Capture of the resultant carbocation by
alkynes provides an efficient route to trisubstituted (E)-alkenyl halides
with high stereoselectivity.
M.-L. Yao, T. R. Quick, Z. Wu, M. P. Quinn, G. W. Kabalka, Org. Lett., 2009,
11, 2647-2649.
A one-pot procedure for the synthesis of 2-alkyl-2-arylcyanoacetates based on a
Pd(OAc)2/dppf-catalyzed enolate arylation followed by in situ
alkylation tolerates a diverse range of aryl and heteroaryl bromides, and
provides a rapid entry to a wide range of products in very good to yield.
X. Wang, A. Guram, E. Bunel, G.-Q. Cao, J. R. Allen, M. M. Faul, J. Org. Chem., 2008,
73, 1643-1645.