Categories: C-O Bond Formation >
Synthesis of diols by dihydroxylation
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A rhodium-catalyzed enantioselective syn addition of bis(catecholato)diboron
to simple alkenes in the presence of (S)-Quinap provides
enantioenriched 1,2-diols after subsequent oxidation. The substrate scope, the reaction mechanism, and competing
pathways are discussed.
S. Trudeau, J. M. Morgan, M. Shrestha, J. P. Morken, J. Org. Chem., 2005,
70, 9538-9544.
Catalytic enantioselective diboration of alkenes is accomplished with readily
available carbohydrate-derived catalysts via the intermediacy of 1,2-bonded
diboronates.
L. Fang, L. Yan, F. Haeffner, J. P. Morken, J. Am. Chem. Soc., 2016,
138, 2508-2511.
Lewis bases catalyze vicinal dioxygenation of olefins with hypervalent iodine
reagents under mild conditions. The reaction tolerates various functional groups.
L. Pan, Z. Ke, Y.-Y. Yeung, Org. Lett., 2021, 23,
8174-8178.
A Pt-catalyzed enantioselective addition of bis(pinacolato)diboron to various
terminal alkenes occurs in the presence of a readily available chiral
phosphonite ligand. While oxidation of the intermediate 1,2-bis(boronate) ester
provides a chiral 1,2-diol as the reaction product, homologation/oxidation
furnishes a chiral 1,4-diol.
L. T. Kliman, S. N. Mlynarski, J. P. Morken, J. Am. Chem. Soc., 2009,
131, 13210-13211.
Iodine catalyzes an environment-friendly and efficient dioxygenation of aryl
alkenes for the construction of vicinal diols in water as solvent with tert-butylhydroperoxide
(TBHP) as the oxidant. The protocol is efficient, sustainable, and operationally
simple. In addition, bisperoxides could be obtained in good yields with Na2CO3
as additive and propylene carbonate as solvent.
X. Gao, J. Lin, L. Zhang, X. Luo, G. Guo, N. Peng, H. Xu, Y. Liu, J. Org. Chem., 2021, 86,
15469-15480.
The use of
bis(pinacolato)diboron enables a palladium-catalyzed alkene diacetoxylation with
oxygen as both
the sole oxidant and oxygen source. This method displayes good functional group tolerance
with good yields and can be applied to late-stage modifications of natural products.
J. Huang, L. Ouyang, J. Li, J. Zheng, W. Yan, W. Wu, H. Jiang, Org. Lett.,
2018, 20, 5090-5093.
A catalytic enantioselective diboration of vinyl boronate esters furnishes
chiral tris(boronates). Subsequent intermolecular or intramolecular deborylative
alkylation occurs in a diastereoselective fashion.
J. R. Coombs, L. Zhang, J. P. Morken,
J. Am. Chem. Soc., 2014,
136, 16140-16143.
An aerobic acetoxyhydroxylation of alkenes is cooperatively catalyzed by organic
nitrite and palladium at room temperature using clean and cheap air as the sole
oxidant. Various vicinal diols, diacetoxyalkanes, and dihalogenoalkanes have
been synthesized.
X.-M. Chen, X.-S. Ning, Y.-B. Kang, Org. Lett.,
2016, 18, 5368-5371.
A platinum-catalyzed hydrosilylation of arylacetylenes with trichlorosilane
followed by a subsequent second hydrosilylation catalyzed by a chiral
monophosphine-palladium complex and an oxidation with hydrogen peroxide gave
1-aryl-1,2-diols of high enantiomeric purity in high yields.
T. Shimada, K. Mukaide, A. Shinohara, J. W. Han, T. Hayashi, J. Am. Chem. Soc., 2002,
124,
1584-1585.
I2-catalyzed oxo-acyloxylation of alkenes and enol ethers with
carboxylic acids provides α-acyloxyketones and esters in high yields. This
unprecedented regioselective oxidative process employs TBHP and Et3N
in stoichiometric amounts under metal-free conditions in DMSO as solvent.
α-Acyloxyketones can be converted in situ to monoprotected diol derivatives in
excellent yields upon treatment with BH3ˇSMe2.
R. N. Reddi, P. K. Prasad, A. Sudalai, Org. Lett.,
2014,
16, 5674-5677.
Aryl iodides are efficient catalysts in an organocatalytic syn
diacetoxylation of alkenes. A broad range of substrates, including electron-rich
as well as electron-deficient alkenes, furnish the desired products in
very good yields with high diastereoselectivity.
W. Zhong, S. Liu, J. Yang, X. Meng, Z. Li, Org. Lett., 2012,
14, 3336-3339.
Addition of perfluoro-tert-butyl alcohol to a toluene solution of
alkene and cyclopropyl malonoyl peroxide increases the rate of dihydroxylation
product formation and the stereoselectivity observed, providing a simple and
effective method for acceleration of this important class of reaction. Basic
hydrolysis of the crude reaction mixture provides access to syn-diols in
high yield and stereoselectivity.
S. Picon, M. Rawling, M. Campbell, N. C. O. Tomkinson, Org. Lett., 2012,
14, 6250-6253.
A clean and efficient and metal-free diacetoxylation reaction of alkenes using
commercially available peroxyacids as the oxidants is catalyzed by triflic acid.
This method enables also oxidative lactonizations of unsaturated carboxylic
acids in good to high yields.
Y.-B. Kang, L. H. Gade, J. Org. Chem., 2012,
77, 1610-1615.
An improved protocol for the RuO4-catalyzed syn-dihydroxylation
uses only 0.5 mol% catalyst under acidic conditions. Various olefins can be
hydroxylated in good to excellent yields with only minor formation of side
products.
B. Plietker, M. Niggemann, Org. Lett., 2003, 3353-3356.
Cyclopropyl malonoyl peroxide, which can be prepared in a single step from the
commercially available diacid, enables an effective dihydroxylation of alkenes
in the presence of water at 40°C. Alkaline hydrolysis of the resulting monoester
leads to the corresponding diol. With 1,2-disubstituted alkenes, the reaction
proceeds with syn selectivity.
J. C. Griffith, K. M. Jones, S. Picon, M. J. Rawling, B. M. Kariuki, M.
Campbell, N. C. O. Tomkinson, J. Am. Chem. Soc., 2010,
132, 14410-14411.
Copper(I) or -(II) salts with weakly coordinating anions catalyze a mild
diacetoxylation of olefins efficiently in the presence of PhI(OAc)2
as the oxidant. The reaction is effective for aryl, aryl alkyl, as well as
aliphatic terminal and olefins forming the corresponding vicinal diacetoxy
compounds in good yields. Internal olefins lead to syn/anti mixtures of up to
5.2.
J. Seayad, A. M. Seayad, C. L. L. Chai, Org. Lett., 2010,
12, 1412-1415.
A palladium-catalyzed diacetoxylation of alkenes in the presence of peracetic
acid and acetic anhydride produces diacetates efficiently and
diastereoselectively. Due to its mild conditions, this method is suitable for a
broad range of substrates encompassing conjugated and nonconjugated olefins.
C. P. Park, J. H. Lee, K. S. Yoo, K. W. Jung, Org. Lett., 2010,
12, 2450-2452.
LiBr is an efficient catalyst for the dihydroxylation of alkenes to afford
either syn or anti diols with excellent diastereoselectivity
depending upon the use of NaIO4 or PhI(OAc)2 as the
oxidants.
L. Emmanuvel, T. M. A. Shaikh, A. Sudalai, Org. Lett.,
2005,
7, 5071-5074.
L. Emmanuvel, T. M. A. Shaikh, A. Sudalai, Org. Lett.,
2005,
7, 5071-5074.
Selective syn and anti diacetoxylations of alkenes have been
achieved using a PhI(OAc)2/BF3ˇOEt2 system in
the presence and absence of water, respectively. A broad range of substrates
including electron-deficient alkenes furnishes the desired products in good to
excellent yields and diastereoselectivity. This novel methodology provides an
alternative approach for the preparation of various 1,2-diols.
W. Zhong, J. Yang, X. Meng, Z. Li, J. Org. Chem., 2011,
76, 9997-10004.
W. Zhong, J. Yang, X. Meng, Z. Li, J. Org. Chem., 2011,
76, 9997-10004.
Grubbs' 2nd generation metathesis catalyst can be used in tandem olefin
metathesis/oxidation protocols. These ruthenium-catalyzed processes provide
access to cis-diols or α-hydroxy ketones from simple olefinic starting
materials.
A. A. Scholte, M. H. An, M. L. Snapper, Org. Lett.,
2006,
8, 4759-4762.
A clean and safe method for the dihydroxylation of alkenes under
organic-solvent- and metal-free conditions was developed. The
resin-supported sulfonic acid is easily recycled.
Y. Usui, K. Sato, M. Tanaka, Angew. Chem. Int. Ed., 2003, 42,
5623-5625.
A two-step sequence of asymmetric dihydroxylation and regioselective
monooxidation gave enantiopure α-hydroxy ketones (acyloins). The
combination of RuCl3/Oxone/NaHCO3 was used in the
first catalytic regioselective oxidation of vic-diols to α-ketols.
B. Plietker, Org. Lett., 2004, 6, 289-291.
TBAI catalyzes an efficient, mild, and regioselective synthesis of
4-aryl/alkyl-1-peroxy-but-3-en-2-ols in good yields from
1-substituted-1,3-butadienes in the presence of hydroperoxides and water. This
regioselective orthogonal dioxygenation of a diene can be executed in a simple
operation and tolerates a wide range of substrates.
A. Kumar, G. N. Khatun, R. A. Fernandes, Org. Lett., 2023, 25,
4313-4317.
A Mo-catalyzed anti-dihydroxylation of secondary allylic alcohols
provides 1,2,3-triols bearing up to three continuous stereocenters with
excellent diastereocontrol. The excellent diastereomeric ratios of the final
triol products can be achieved due to the high level of both diastereocontrol in
the initial epoxidation and regiocontrol in the following hydrolysis in situ.
S. Su, C. Wang,
Org. Lett., 2019, 21, 2436-2440.
A biologically inspired cis-dihydroxylation of a wide range of olefins
using inexpensive and readily available mononuclear non-heme manganese complexes
bearing tetradentate nitrogen-donor ligands and aqueous hydrogen peroxide (H2O2)
and potassium peroxymonosulfate (KHSO5) as terminal oxidants provides
cis-diols in practically useful yields and enantioselectivity.
J. Chen, J. Zhang, Y. Sun, Y. Xu, Y. Yang, Y.-M. Lee, W. Ji, B. Wang, W. Nam,
B. Wang, J. Am. Chem. Soc.,
2023, 145, 27626-27638.
An efficient and cost-effective cis-dihydroxylation reaction of acrylate
derivatives in acetone with an imidazolium salt as catalyst and KMnO4
as the oxidant provides dihydroxylated products without overoxidation. This
non-aqueous protocol is highly suitable for the large-scale preparation of
cis-dihydroxylated compounds.
I. Khan, Z.-B. Luo, A. Valeru, Y. Xu, B. Liu, B. Sangepu, J.-M. Xie, Synthesis, 2018, 50,
1815-1819.
An efficient and economic procedure for the dihydroxylation of various olefin
derivatives with commercial KMnO4 as the oxidant in the presence of a
quaternary ammonium salt is suitable for large-scale production of cis-dihydroxy
compounds, even those bearing primary and secondary alcohol groups, without
overoxidation.
Z.-b. Luo, C. Zhao, J. Xie, H.-f. Lu, Synthesis, 2016,
48, 3696-3700.
A dioxygenation of alkenes using molecular oxygen and a simple, readily prepared
hydroxamic acid derivative in th presence of a radical initiator offers an
alternative to common dioxygenation processes catalyzed by precious transition
metals. This transformation capitalizes on the unique reactivity profile of
hydroxamic acid derivatives in radical-mediated alkene addition processes.
B. C. Giglio, V. A. Schmidt, E. J. Alexanian, J. Am. Chem. Soc., 2011,
133, 13320-13322.