Categories: C-O Bond Formation > Synthesis of alcohols (hydroxylation) >
Synthesis of benzyl alcohols
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Recent Literature
The use of bis(methanesulfonyl) peroxide as an oxidant enables a selective
synthesis of benzylic alcohols without further oxidation of alcohols to ketones.
A proton-coupled electron transfer mechanism (PCET) may account for the
difference in reactivity.
L. Tanwar, J. Börgel, T. Ritter, J. Am. Chem. Soc.,
2019, 141, 17983-17988.
A Cu/2,2′-biquinoline catalyst mediates a benzylic C-H esterification with
limiting C-H substrate. Blue-light irradiation promotes carboxylate-to-copper
charge transfer, reducing resting-state CuII to CuI, which
activates the peroxide to generate an alkoxyl radical hydrogen-atom-transfer
species. This "photochemical redox buffering" sustains the activity of Cu
catalysts in radical-relay reactions.
D. L. Golden, C. Zhang, S.-J. Chen, A. Vasilopoulos, I. A. Guzei, S. S. Stahl, J. Am. Chem. Soc.,
2023, 145, 9434-9440.
Diverse alcohols were synthesized by metal-free coupling of diazoalkanes derived
from p-toluenesulfonylhydrazones to water under reflux and microwave
conditions, in high yields. In addition, this protocol was successfully applied
in the synthesis of deuterium-labeled alcohols using deuterium oxide.
Á. García-Muñoz, A. I. Ortega-Arizmendi, M. A. García-Carrillo, E. Díaz, N.
Gonzalez-Rivas, E. Cuevas-Yañez, Synthesis, 2012, 44,
2237-2242.
The use of Oxone allows the conversion of various aryl-, heteroaryl-, alkenyl-,
and alkyltrifluoroborates into the corresponding oxidized products in excellent
yields. This method tolerates a broad range of functional groups, and in
secondary alkyl substrates it was demonstrated to be completely stereospecific.
G. A. Molander, L. N. Cavalcanti, J. Org. Chem., 2011,
76, 623-630.
A visible light-induced photocatalysis enables a general and practical
decarboxylative hydroxylation of a broad range of carboxylic acids using
molecular oxygen as the green oxidant. NaBH4 as additive reduces
unstable peroxyl radical intermediates in situ.
S. N. Khan, M. K. Zaman, R. Li, Z. Sun, J. Org. Chem., 2020, 85,
5019-5026.
A photocatalytic direct decarboxylative hydroxylation of carboxylic acids
enables the conversion of various readily available carboxylic acids to alcohols
in good yields under extremely mild reaction conditions using molecular oxygen
as a green oxidant and visible light as a driving force.
H.-T. Song, W. Ding, Q.-Q. Zhou, J. Liu, L.-Q. Lu, W.-J. Xiao, J. Org. Chem.,
2016, 81, 7250-7255.
Ubiquitous carboxylic acids can serve as starting materials for a
photocatalytic decarboxylative C-O bond formation reaction that provides rapid
and facile access to the corresponding acetoxylated products.
S. Senaweera, K. C. Cartwrigt, J. A. Tunge, J. Org. Chem., 2019, 84,
12334-12343.
A formic acid promoted hydration of readily available alkynes followed by an
iridium-catalyzed transfer hydrogenation under mild conditions provides
alcohols. This transformation is simple, efficient, and can be performed with a
variety of alkynes in good yields and with excellent stereoselectivities.
N. Luo, Y. Zhong, J.-T. Liu, L. Ouyang, R. Luo, Synthesis, 2020, 52,
3439-3445.
Two complementary dual catalytic systems enable a highly regioselective
reductive hydration of terminal alkynes to yield branched or linear alcohols in
very good yield. The method is compatible with terminal, di-, and trisubstituted
alkenes. This reductive hydration constitutes a strategic surrogate to alkene
oxyfunctionalization and may be of utility in multistep settings.
L. Li, S. B. Herzon, J. Am. Chem. Soc., 2012,
134, 17376-17378.
The neutral gold(I) complex [(IPr)AuCl] is a highly effective catalyst for the
regioselective hydration of terminal alkynes, including aromatic alkynes and
aliphatic alkynes providing methyl ketones in high yields. Furthermore,
optically active alcohols could be obtained in high yields with very good
enatioselectivities via one-pot sequential hydration/asymmetric transfer
hydrogenation using Cp*RhCl[(R,R)-TsDPEN] as additional catalyst.
F. Li, N. Wang, L. Lu, G. Zhu, J. Org. Chem.,
2015,
80, 3538-3546.
In a rhenium-catalyzed oxyalkylation of alkenes, hypervalent iodine(III)
reagents derived from widely occurring aliphatic carboxylic acids were not only
an oxygenation source but also an alkylation source via decarboxylation. The
reaction offers a wide substrate scope, totally regiospecific
difunctionalization, mild reaction conditions, and ready availability of both
substrates.
Y. Wang, L. Zhang, Y. Yang, P. Zhang, Z. Du, C. Wang, J. Am. Chem. Soc., 2013,
135, 18048-18051.
Various tertiary β-trifluoromethyl alcohols can be synthesized in good yields
without transition metal catalysts via a radical trifluoromethylation of alkenes
using in situ generated peroxide in NMP under O2 as the radical
initiator.
C. Liu, Q. Lu, Z. Huang, J. Zhang, F. Liao, P. Peng, A. Lei, Org. Lett.,
2015,
17, 6034-6037.
A convenient and metal-free three-component oxychalcogenation reaction of
alkenes, diselenides/thiophenols, and H2O/alcohols provides
β-hydroxyl or β-alkoxy organochalcogenides in very good yields.
Tetrabutylammonium tribromide (TBATB) and dimethylsulfoxide (DMSO) are utilized
as the catalyst and the terminal oxidant, respectively.
J. Huang, X. Li, L. Xu, Y. Wei, J. Org. Chem., 2023, 88,
3054-3067.
A visible light-promoted and tertiary-amine-assisted hydroxysulfenylation of
both electron-rich and electron-deficient alkenes with thiophenols provides
β-hydroxysulfides in very good yields. This simple and sustainable approach
features mild reaction conditions, high efficiency, and excellent functional
group tolerance.
J. Shi, X.-W. Gao, Q.-X. Tong, J.-J. Zhong, J. Org. Chem., 2021, 86,
12922-12931.
Related
An esterification of primary benzylic C-H bonds with carboxylic acids using di-tert-butyl
peroxide as an oxidant is catalyzed by novel ionic iron(III) complexes
containing an imidazolinium cation. The reaction offers a broad generality and
tolerates sterically hindered starting materials.
B. Lu, F. Zhu, H.-M. Sun, Q. Shen, Org. Lett.,
2017, 19, 1132-1135.
An efficient phosphorylation of C(sp3)-H bonds of readily available
methyl arenes with diaryl phosphinic acids proceeds efficiently under
transition-metal-free reaction conditions via Bu4NI-catalyzed
dehydrogenative coupling to provide valuable organophosphorus compounds.
B. Xiong, G. Wang, C. Zhou, Y. Liu, P. Zhang, K. Tang, J. Org. Chem.,
2018, 83, 993-999.
A highly efficient dynamic kinetic resolution (DKR) of
secondary alcohols at room temperature was developed. In situ racemization of
substrates using a Ru catalyst and lipase-catalyzed acylation provides
enantiopure products in high yields in very short reaction times. The use of
isopropenyl acetate as the acyl donor makes the purification of the products
very easy.
B. Martin-Matute, M. Edin, Krisztian Bogar, J.-E. Baeckvall, Angew. Chem.
Int. Ed.,
2004,
43, 6535-6539.
Well-defined 16-electron ruthenium complexes bearing an N-heterocyclic carbene
ligand are active catalysts in the racemization of chiral alcohols. Mechanistic
considerations are presented.
J. Bosson, S. P. Nolan, J. Org. Chem., 2010,
75, 2039-2043.