Categories: C-O Bond Formation > Synthesis of alcohols (hydroxylation) >
Synthesis of allyl alcohols
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A catalytic regio- and stereoselective 1,4-hydroboration with pinacolborane in
the presence of Ni(cod)2 and PCy3 exhibits broad substrate
scope operating on a range of substituted 1,3-dienes and occurs with generally
high levels of selectivity and efficiency. The intermediate allylboronate can be
oxidized to stereodefined allylic alcohols or can be used in stereoselective
carbonyl addition reactions.
R. J. Ely, J. P. Morken, J. Am. Chem. Soc., 2010,
132, 2534-2535.
Use of 4,5-diazafluorenone as an ancillary ligand for Pd(OAc)2
enables terminal alkenes to be converted to linear allylic acetoxylation
products in good yields and selectivity under O2. Mechanistic studies
have revealed that the ligand facilitates C-O reductive elimination from a
π-allyl-PdII intermediate, thereby eliminating the requirement for benzoquinone
as stoichiometric oxidant in this key catalytic step.
A. N. Campbell, P. B. White, I. A. Guzei, S. S. Stahl, J. Am. Chem. Soc., 2010,
132, 15116-15119.
The combination of a bidentate-sulfoxide-ligated palladium complex
and Ag2CO3 catalyzes an allylic C-H acyloxylation of
terminal alkenes with 4-nitrobenzoic acid in the presence of 1,4-benzoquinone
under mild reaction conditions. Ag2CO3 as an additive and
4-nitrobenzoic acid as a carboxylate source were essential to exhibiting high
catalytic activity and regioselectivity.
A. Skhiri, H. Nagae, H. Tsurugi, M. Seki, K. Mashima, Org. Lett., 2021, 23,
7044-7048.
Pd(OAc)2, sulfoxide-oxazoline (sox) as a ligand and benzoquinone as
an oxidant enable a ligand-controlled branch-selective allylic C-H
carboxylation. The developed catalytic system couples terminal alkenes and
carboxylic acids to furnish the corresponding branched allylic esters with high
regioselectivity.
H. Kondo, F. Yu, J. Yamaguchi, G. Liu, K. Itami, Org. Lett.,
2014,
16, 4212-4215.
Sodium perborate (SPB), a principal component of washing powders, can be used as
an inexpensive and eco-friendly oxidant in the palladium-catalyzed C-H
acyloxylation of alkenes in excellent regio- and stereochemistry. The reactions
used anhydrides as acyloxy sources. The method enables the conversion of both
terminal and internal alkenes, and allows even benzylic C-H oxidation.
L. T. Pilarski, P. G. Janson , K. J. Szabó, J. Org. Chem., 2011,
76, 1503-1506.
An oxidative decarboxylation of β,γ-unsaturated carboxylic acids mediated by
PhI(OAc)2 gives the corresponding allylic acetates. In addition, a
decarboxylative C-N bond formation was achieved. Mechanistic studies suggest an
unique reactivity of hypervalent iodine reagents in this ionic oxidative
decarboxylation.
K. Kiyokawa, S. Yahata, T. Kojima, S. Minakata, Org. Lett.,
2014,
16, 4646-4649.
A Pd(TFA)2-catalyzed 1,3-isomerization of tertiary allylic alcohols
gives secondary allylic alcohols. In a one-pot procedure, a subsequent Pd(TFA)2/neocuproine-catalyzed
oxidation leads to β-disubstituted-α,β-unsaturated enones directly.
J. Li, C. Tan, J. Gong, Z. Yang, Org. Lett.,
2014,
16, 5370-5373.
Hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement
(n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions
joined isolated C-C double or triple bonds to generate conjugated polyene or
enyne structure motifs. The polyene natural product navenone B has been
constructed by iterative use of a Grignard reaction, a 1,3-rearrangement of the
resulting allylic alcohol, and subsequent oxidation.
P.-F. Li, H.-L. Wang, J. Qu, J. Org. Chem., 2014,
79, 3955-3962.
The combination of a vanadium-oxo compound with a lipase enables the regio- and
enantioconvergent transformation of racemic allyl alcohols into optically active
allyl esters. In this dynamic kinetic resolution, the vanadium compounds
catalyzes both the racemization and the transposition of the hydroxyl group,
while the lipase effects the chemo- and enantioselective esterification.
S. Akai, R. Hanada, N. Fujiwara, Y. Kita, M. Egi, Org. Lett., 2010,
12, 4900-4903.
Trichloroacetimidates of allylic alcohols, either generated in situ or in a
separate step, undergo clean enantioselective SN2′ substitution with
various carboxylic acids in the presence of a chiral palladium(II) catalyst. The
scope and limitations of this useful catalytic asymmetric allylic esterification
are defined.
J. S. Cannon, S. F. Kirsch, L. E. Overman, J. Am. Chem. Soc., 2010,
132, 15185-15191.
A copper-catalyzed formal SN2' defluorinative borylation of
3-substituted 3,3-difluoropropenes provides 3-fluoroallylboronic esters in high
yields with excellent Z:E ratios. The primary 3-fluoroallylboronic esters
undergo several synthetic sequences involving sigmatropic rearrangements, SE2'
substitutions, and SN2' substitutions to give tertiary allylic
fluorides.
T. W. Butcher, J. L. Yang, J. F. Hartwig,
Org. Lett., 2020, 22, 6805-6809.
The cooperative interaction of a diselane and a photoredox catalyst enables a
metal-free protocol for the oxidative coupling of nonactivated alkenes with
simple carboxylic acids in ambient air or pure O2 as the terminal
oxidant. A range of both functionalized and nonfunctionalized alkenes can be
readily converted into the corresponding allylic ester with good yields and
excellent regioselectivity as well as good functional group tolerance.
S. Ortgies, C. Depken, A. Breder, Org. Lett.,
2016, 18, 2856-2859.
4-Hydroxyalk-2-en-1-ones as highly functionalized four-carbon units can
conveniently be prepared by Knoevenagel reactions of aldehydes with
1-(arylsulfinyl)alkan-2-ones in the presence of diethylamine. The reaction
tolerates carbonyl and hydroxy groups in both of the alkyl chains.
J. Nokami, K. Kataoka, K. Shiraishi, M. Osafune, I. Hussain, S.-i. Sumida, J. Org. Chem., 2001,
66, 1228-1232.
A dynamic kinetic asymmetric transformation (DYKAT) process constitutes a
reasonable alternative strategy to access versatile Baylis-Hillman derivatives
in highly enantiomerically enriched form. By using an oxygen nucleophile that
can become a hydroxyl group, the process constitutes a deracemization.
B. M. Trost, H.-C. Tsui, F. D. Toste, J. Am. Chem. Soc., 2000,
122, 3534-3535.
An enantioselective nickel-catalyzed borylative coupling of
1,3-dienes with aldehydes provides an efficient route to highly valuable
homoallylic alcohols in a single step. Enabled
by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields
products with exceptional diastereoselectivity, E-selectivity, and
enantioselectivity.
J.-T. Ma, T. Zhang, B.-Y. Yao, L.-J. Xiao, Q.-L. Zhou, J. Am. Chem. Soc.,
2023, 145, 19195-19201.
An enantioselective nickel-catalyzed borylative coupling of
1,3-dienes with aldehydes provides an efficient route to highly valuable
homoallylic alcohols in a single step. Enabled
by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields
products with exceptional diastereoselectivity, E-selectivity, and
enantioselectivity.
J.-T. Ma, T. Zhang, B.-Y. Yao, L.-J. Xiao, Q.-L. Zhou, J. Am. Chem. Soc.,
2023, 145, 19195-19201.
A chiral α-borylmethyl-(Z)-crotylboronate reagent enables highly stereo- and
enantioselective syntheses of (E)-δ-hydroxymethyl-syn-homoallylic
alcohols via aldehyde allylboration and a subsequent oxidative workup.
J. Liu, S. Gao, M. Chen, Org. Lett., 2021, 23,
9451-9456.
Chiral phosphine-catalyzed coupling of two readily available partners,
γ-aryl-substituted alkynoates and alcohols, under mild conditions enables the
enantioselective synthesis of benzylic ethers via internal redox reaction of the
alkynoate partner.
D. T. Ziegler, G. C. Fu, J. Am. Chem. Soc., 2016,
138, 12069-12072.
A mild and operationally simple copper-catalyzed vinylogous aerobic oxidation of
β,γ- and α,β-unsaturated esters features good yields, broad substrate scope,
excellent chemo- and regioselectivity, and good functional group tolerance. This
method is additionally capable of oxidizing β,γ- and α,β-unsaturated aldehydes,
ketones, amides, nitriles, and sulfones.
H.-J. Zhang, A. W. Schuppe, S.-T. Pan, J.-X. Chen, B.-R. Wang, T. R. Newhouse,
L. Yin, J. Am. Chem. Soc.,
2018,
140, 5300-5310.
A copper(II)-catalyzed intermolecular three-component oxyarylation of allenes
using arylboronic acids as a carbon source and TEMPO as an oxygen source
proceeded under mild conditions with high regio- and stereoselectivity and
functional group tolerance.
T. Itoh, Y. Shimizu, M. Kanai, Org. Lett., 2014,
16, 2736-2739.
A general, Ir(I)-catalyzed enantioselective decarboxylative allylic
etherification of aryl allyl carbonates provides aryl allyl ethers with high
stereoselection.
D. Kim, S. Reddy, O. V. Singh, J. S. Lee, S. B. Kong, H. Han, Org. Lett., 2013,
15, 512-515.
The allylic oxidation of cyclic alkenes with a copper-aluminum mixed oxide as
catalyst in the presence of a carboxylic acid and tert-butyl
hydroperoxide as the oxidant gives the corresponding allylic esters. When
l-proline is employed, the allylic alcohol or ketone is obtained.
A. L. García-Cabeza, R. Marín-Barrios, F. J. Moreno-Dorado,
M. J. Ortega, G. M. Massanet, F. M. Guerra, Org. Lett., 2014,
16, 1598-1601.
An enzyme acylation catalyst and a heterogeneous Brřnsted acid as an
isomerization/racemization catalyst enables a migratory dynamic kinetic
resolution of readily available carbocyclic tertiary carbinols to yield allylic
esters in high yield with excellent stereoselectivity. An easy-to-use teabag
setup combining resin-bound catalysts, a biphasic isooctane-water solvent system,
and a highly lipophilic acyl donor efficiently suppresses side reactions.
C. M. Sapu, T. Görbe, R. Lihammar, J.-E. Bäckvall, J. Deska, Org. Lett.,
2014,
16, 5952-5955.
A regio- and diastereoselective nickel-catalyzed reductive coupling of
carbonyls with dienes in the presence of a stoichiometric amount of
bis(pinacolato)diboron furnishes allyl boronic esters as the reaction product,
which was readily converted to the derived allylic alcohol by oxidative workup.
H. Y. Cho, J. P. Morken, J. Am. Chem. Soc., 2008,
130, 16140-16141.
Pt-catalyzed enantioselective addition of
bis(pinacolato)diboron (B2(pin)2) to conjugated dienes
enables an asymmetric 1,4-dihydroxylation of 1,3-dienes. Dienes which are unable to adopt the
S-cis conformation are unreactive. For most substrates, 1,4-addition is the
predominant pathway.
H. E. Burks, L. T. Kliman, J. P. Morken, J. Am. Chem. Soc., 2009,
131, 9134-9135.
A catalytic stereoselective 1,4-diboration of conjugated dienes with B2(pin)2
and the presence of Ni(cod)2 and PCy3 as the catalyst
roceeds efficiently at low catalyst loadings and broadens the substrate scope of
current methods for catalytic diene diboration by including internal and
sterically hindered. The intermediate allylboronate was oxidized to the
stereodefined allylic 1,4-diol.
R. J. Ely, J. P. Morken, Org. Lett., 2010,
12, 4348-4351.
An enantioselective 1,4-diboration of cyclic dienes with a new taddol-derived
phosphonite ligand and subsequent oxidation delivers 1,4-diols with excellent
enantioselectivity, whereas homologation can be used to deliver chiral
1,6-diols.
K. Hong, J. P. Morken, J. Org. Chem., 2011,
76, 9102-9108.
The presence of a base strongly improves the efficiency and the selectivity of
the Pd-catalyzed oxidation of terminal alkenes in carboxylic acids. The
methodology is particularly well adapted for the oxidation of homoallylic
alcohols, for which the resulting acyloxylated products are obtained selectively
as E-isomers in good yields.
E. Thiery, C. Aouf, J. Belloy, D. Harakat, J. Le Bras, J. Muzart, J. Org. Chem., 2010,
75, 1771-1774.
Commercially available and very inexpensive benzoic acids catalyze an efficient
and simple isomerization of readily prepared allylic alcohols to yield cyclic
products, unusual enyne, and dienols. The catalysts can be tuned for reactivity
and substrate sensitivity.
J. A. McCubbin, S. Voth, O. V. Krokhin, J. Org. Chem., 2011,
76, 8537-8542.
O3ReOSiPh3 promotes the 1,3-isomerization of various
allylic alcohols. Two different strategies allow the selective formation of
a single isomer. The first strategy utilizes the formation of a conjugated
alkene to ensure a high selectivity. The second strategy employs N,O-bis(trimethylsilyl)acetamide
(BSA) as an additive to remove the product from the reaction equilibrium and
works well for the isomerization of tertiary allylic alcohols.
C. Morrill, R. H. Grubbs, J. Am. Chem. Soc.,
2005,
127, 2842-2843.
C. Morrill, R. H. Grubbs, J. Am. Chem. Soc.,
2005,
127, 2842-2843.
A method for the preparation of a wide range of branched allylic esters from
terminal alkynes proceeds via a redox-neutral propargylic CH activation
employing a rhodium(I)/DPEphos catalyst.
A. Lumbroso, P. Koschker, N. R. Vautravers, B. Breit, J. Am. Chem. Soc., 2011,
133, 2386-2389.
A hydroxyl group-directed, highly regio- and stereoselective transposition of
allylic alcohols based on rhenium catalysis is suitable for a direct
isomerization of acetals into the thermodynamically preferred isomer as long as
one of the hydroxyl groups is allylic. This method will expand the scope of
rhenium-catalyzed alcohol transpositions for complex molecule synthesis.
A. T. Herrmann, T. Saito, C. E. Stivala, J. Tom, A. Zakarian, J. Am. Chem. Soc., 2010,
132, 5962-5963.
Gold N-heterocyclic carbene complexes, in conjunction with a
silver salt, were found to efficiently catalyze the rearrangement of allylic
acetates under both conventional and microwave-assisted heating. The steric hindrance of
the ligand bound to gold was found crucial as
only extremely bulky ligands permitted the isomerization.
N. Marion, R. Gealageas, S. P. Nolan, Org. Lett., 2007,
9, 2653-2656.
Efficient and stereoselective rearrangement catalyzed by only one mole-percent
gold(I) chloride/silver(I) trifluoromethanesulfonate of Baylis-Hillman acetates
afforded 2-(acetoxymethyl)alk-2-enoates under mild reaction conditions in very
good yields with 100% E-selectivity.Cyclohex-2-enone derived
Baylis-Hillman acetates gave 2-alkylidenecyclohex-3-enones by elimination of
acetic acid.
Y. Liu, D. Mao, J. Qian, S. Lou, Z. Xu, Y. Zhang, Synthesis, 2009,
1170-1174.
Related
Catalytic access to thermodynamically less stable Z-alkenes have relied upon
kinetic control of the reaction. A mild and simple orthogonal approach proceeds
via photochemically catalyzed isomerization of the thermodynamic E-alkene
to the less stable Z-isomer via a photochemical pumping mechanism.
K. Singh, S. J. Staig, J. D. Weaver, J. Am. Chem. Soc., 2014,
136, 5275-5278.
In the presence of a 1:1 mixture of n-butyllithium and lithioacetonitrile
in THF, a series of styrene oxides can be converted into one-carbon homologated
allyl alcohols in an unusual regioselective manner.
T. Tomioka, R. Sankranti, T. Yamada, C. Clark, Org. Lett., 2013,
15, 5099-5101.
A combination of a lipase and a ruthenium complex reaction enables a dynamic
kinetic resolution of allylic alcohols in which racemic substrates react in the
presence of an acyl donor to allylic acetates of high optical purity in very
good yields.
D. Lee, E. A. Huh, M.-J. Kim, H. M. Jung, J. H. Koh, J. Park,
Org. Lett., 2000, 2, 2377-2379.
The combination of PdCl2 and DMA allows highly effective oxygenation of terminal olefins under cocatalyst-free conditions. The use of a different nucleophile (H2O, AcOH) can lead to a complete switch in regioselectivity between C1 and C2 positions.
T. Mitsudome, T. Umetani, N. Nosaka, K. Mori, T. Mizugaki, K. Ebitani, K.
Kaneda, Angew. Chem. Int. Ed., 2006,
45, 481-485.
H. Miyabe, K. Yoshida, M. Yamauchi, Y. Takemoto, J. Org. Chem., 2005,
70, 2148-2153.