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Synthesis of aryl ethers
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Two types of ligands promote Cu-catalyzed alkoxylations of (hetero)aryl
halides to provide alkyl aryl ethers. In case of coupling with aryl chlorides
and bromides, two oxalic diamides serve as the powerful ligands. In addition,
tert-butoxide enables a Cu-catalyzed alkoxylation of aryl iodides at room
temperature.
Z. Chen, Y. Jiang, L. Zhang, Y. Guo, D. Ma, J. Am. Chem. Soc.,
2019,
141, 3541-3549.
Self-assembled octanuclear copper clusters catalyzed
the coupling of aryl iodides with alcohols under mild
conditions. Reactions involving low catalyst loadings (0.4%) and tetrahydrofurfuryl alcohol were typically
complete in 4-8 h at 110°C using an oil bath or 1-3 h with microwave heating.
G. F. Manbeck, A. J. Lipman, R. A. Stockland, A. L. Freidl, A. F. Hasler, J.
J. Stone, I. A. Guzei, J. Org. Chem., 2005,
70, 244-250.
The use of 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4Phen) as a
ligand improves the Cu-catalyzed cross-coupling reactions of aryl iodides and
bromides with primary and secondary aliphatic, benzylic, allylic, and
propargylic alcohols. The relatively mild conditions, tolerate a wide array of
functional groups on both the electrophilic and nucleophilic coupling partners.
R. A. Altman, A. Shafir, P. A. Lichtor, S. L. Buchwald, J. Org. Chem., 2008,
73, 284-286.
In an efficient and mild copper-catalyzed ether formation from aryl halides and
aliphatic alcohols, the key to a successful coupling is the use of lithium
alkoxide, directly or in situ generated by lithium tert-butoxide, and the
corresponding alcohol as solvent.
J. Huang, Y. Chen, J. Chan, M. L. Ronk, R. D. Larsen, M. M. Faul, Synlett, 2011,
1419-1422.
Ullmann-type coupling reactions of aryl iodides and aliphatic alcohols occur at
110 °C with N,N-dimethylglycine as the ligand, giving aryl alkyl ethers
in high yields.
H. Zhang, D. Ma, W. Cao, Synlett, 2007, 243-246.
A simple and mild coupling method of aryl iodides and aliphatic alcohols,
which does not require alkoxide bases, can be performed in neat alcohol or
toluene as solvent. An optically active benzylic alcohol underwent the reaction
with complete retention of configuration.
M. Wolter, G. Nordmann, G. E. Job, S. L. Buchwald, Org.
Lett., 2002, 4, 973-976.
The use of biaryl phosphine ligand was key to achieving efficient
cross-coupling of (hetero)aryl chlorides with near-equimolar amounts of
secondary alcohols. An unusual reactivity difference between an electron-rich
aryl bromide and the analogous aryl chloride was observed.
H. Zhang, P. Ruiz-Castillo, A. W. Schuppe, S. L. Buchwald,
Org. Lett., 2020, 22, 5369-5374.
Transition-metal-free arylation of tertiary alcohols with ortho-substituted
diaryliodonium salts enables the synthesis of tertiary alkyl aryl ethers of
previously unprecedented steric congestion. Cyclic and acyclic aliphatic,
benzylic, allylic, and propargylic tertiary alcohols as well as primary and
secondary fluorinated alcohols can be converted.
E. Lindstedt, E. Stridfeldt, B. Olofsson, Org. Lett.,
2016, 18, 4234-4237.
An arylation of allylic and benzylic alcohols with diaryliodonium salts
yields alkyl aryl ethers under mild and metal-free conditions. Phenols are
arylated to diaryl ethers in good to excellent yields. The reaction employs
diaryliodonium salts and sodium hydroxide in water at low temperature, and avoids the use of excess amounts of the coupling partners.
E. Lindstedt, R. Ghosh, B. Olofsson, Org. Lett., 2013,
15, 6070-6073.
Palladium-catalzyed reactions of aryl halides including activated, nonactivated,
and (hetero)aryl bromides as well as aryl chlorides with primary alcohols gave
the corresponding alkyl aryl ethers in high yield in the presence of a bulky
di-1-adamantyl-substituted bipyrazolylphosphine ligand. Functionalizations of
primary alcohols in the presence of secondary and tertiary alcohols proceed with
excellent selectivity.
S. Gowrisankar, A. G. Sergeev, P. Anbarasan, A. Spannenberg, H. Neumann, M.
Beller, J. Am. Chem. Soc., 2010,
132, 11592-11598.
A general Pd-catalyzed coupling of methanol with (hetero)aryl halides proceeds
under mild conditions with a wide range of aryl and heteroaryl halides to give
methyl aryl ethers in high yield.
C. W. Cheung, S. L. Buchwald, Org. Lett., 2013,
15, 3966-3969.
A one-pot method for the preparation of alkyl aryl ethers from aryl halides
and the preparation of substituted benzofurans via a Pd-catalyzed phenol
formation/cyclization protocol starting from 2-chloroaryl alkynes are
described.
K. W. Anderson, T. Ikawa, R. E. Tundel, S. L. Buchwald, J. Am. Chem. Soc., 2006,
128, 10694-10695.
A formal cross-coupling of aryl methyl sulfones and alcohols affords alkyl
aryl ethers via an SRN1 pathway. A dimsyl-anion initiated radical
chain process was revealed as the major pathway.
J. Bai, T. Wang, B. Dai, Q. Liu, P. Yu, T. Jia, Org. Lett., 2021, 23,
5761-5765.
A palladium-catalyzed synthesis of aryl tert-butyl ethers from a
variety of unactivated aryl bromides or chlorides is described. The ether
products, which are precursors to phenols, are obtained in very good yield
in the presence of air-stable dialkylphosphinobiphenyl ligands.
C. A. Parrish, S. L. Buchwald, J. Org. Chem., 2001,
66, 2498-2500.