Categories: C-O Bond Formation >
Synthesis of diols by dihydroxylation
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Recent Literature
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.
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.
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.
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.
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.
L. Emmanuvel, T. M. A. Shaikh, A. Sudalai, Org. Lett.,
2005,
7, 5071-5074.
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.
