Categories: C-S Bond Formation > Synthesis of sulfones >
Synthesis of allylic sulfones
Recent Literature
A dehydrative sulfination of allylic alcohols provides allylic sulfones under
mild reaction conditions in very good yields in an environmentally friendly
manner, yielding water as the only byproduct. The reaction tolerates a wide
range of functional groups. In gram scale reactions, allylic sulfones could be
conveniently isolated in high yield by filtration.
P. Xie, Z. Sun, S. Li, X. Cai, J. Qiu, W. Fu, C. Gao, S. Qu, X. Yang, T.-P.
Loh,
Org. Lett., 2020, 22, 4893-4897.
Formation of allyl phenyl sulfones with excellent yields from allylic alcohols
was promoted by a combination of Pd(OAc)2, PPh3, and
Et3B via in situ activation of the alcohol group.
S. Chandrasekhar, V. Jagadeshwar, B. Saritha, C. Narsihmulu, J. Org. Chem., 2005, 70, 6506-6507.
A complex of readily
available (CH3CN)3W(CO)3 and a bipyridine
ligand catalyzes an allylation of sodium sulfinates at 60°C to provide branched
allylic sulfones in very good yields and excellent regioselectivity.
Y. Xu, M. Salman, S. Khan, J. Zhang, A. Khan, J. Org. Chem., 2020, 85,
11501–11510.
In the presence of a Pd catalyst and excess boric acid, a range of α-unbranched
primary allylic amines were smoothly substituted with sodium sulfinates in an
α-selective fashion to give structurally diverse allylic sulfones in good to
excellent yields with exclusive E selectivity. Use of BINOL as a ligand
allowed the transformation of unsymmetric α-chiral primary allylic amines in
good to excellent yields with excellent retention of ee.
X.-S. Wu, Y. Chen, M.-B. Li, M.-G. Zhou, S.-K. Tian, J. Am. Chem. Soc., 2012,
134, 14694-14697.
A chemodivergent protocol for Pd-catalyzed and ligand-controlled coupling of
allenes with sulfinic acids provides straightforward and atom-economical access
to branched allylic sulfones and linear allylic sulfones in good yields with
high selectivities. This strategy features mild conditions, an unprecedented
substrate scope, and functional group compatibility.
J. Zhang, Y. Wang, C. You, M. Shi, X. Mi, S. Luo, Org. Lett.,
2022, 24, 1186-1189.
A Rh(I)/DPEphos/benzoic acid catalyst system enables the transformation of
terminal alkynes with sulfonyl hydrazides to produce branched allylic sulfones
with very good yields and selectivities.
K. Xu, V. Khakyzadeh, T. Bury, B. Breit,
J. Am. Chem. Soc., 2014,
136, 16124-16127.
The addition of Grignard reagents or organolithium reagents to the SO2-surrogate
DABSO generates a diverse set of metal sulfinates, which can be trapped in situ
with a wide range of C-electrophiles, including alkyl, allyl, and benzyl halides,
epoxides, and (hetero)aryliodoniums to give sulfone products.
A. S. Deeming, C. J. Russell, A. J. Henessy, M. C. Willis, Org. Lett., 2014,
16, 150-153.
An iridium-catalyzed allylation of various sodium sulfinates with achiral
allylic carbonates occurs in good yields, with high selectivity for the branched
isomer, and high enantioselectivities (up to 98% ee).
M. Ueda, J. F. Hartwig, Org. Lett., 2010,
12, 88-91.
Regiospecific radical reactions of β-alkyl nitroalkenes with sulfonyl hydrazides
provide allyl sulfones with high regioselectivity in the presence of
dimethylformamide (DMF), whereas reactions in acetonitrile provide vinyl
sulfones.
Y. Wang, G. Xiong, C. Zhang, Y. Chen, J. Org. Chem., 2021, 86,
4018-4026.
A (R)-DTBM-Segphos/Pd-catalyzed regio- and enantioselective
hydrosulfonylation of 1,3-dienes with sulfinic acids provides atom- and
step-economical access to 1,3-disubstituted chiral allylic sulfones. The
reaction occurs under mild conditions and has a broad substrate scope.
Q. Zhang, D. Dong, W. Zi, J. Am. Chem. Soc.,
2020, 142, 15654-15660.
A one-pot synthesis of aryl sulfones from primary alcohols is described.
Alcohols were treated with N-bromosuccinimide and triphenylphosphine,
followed by addition of sodium arenesulfinate with a catalytic amount of
tetrabutylammonium iodide to afford the aryl sulfones in good to high yields.
T. Murakami, K. Furusawa, Synthesis, 2002, 479-482.
A modular, practical,
and general palladium-catalyzed, radical three-component coupling enables selective
1,4-difunctionalization of unactivated 1,3-dienes, such as butadiene, by employing different commercially available nitrogen-, oxygen-,
sulfur-, or carbon-based nucleophiles and unactivated alkyl bromides.
H.-M. Huang, P. Bellotti, P. M. Pfüger, J. L. Schwarz, B. Heidrich, F.
Glorius, J. Am. Chem. Soc.,
2020, 142, 10173-10183.
In the absence of external catalysts and additives, a broad range of benzylic
and allylic alcohols react with various sulfinyl chlorides to afford
structurally diversified benzylic and allylic sulfones in moderate to excellent
yields. A catalysis with byproduct HCl is involved in this new protocol.
H.-H. Li, D.-J. Dong, Y.-H. Jin, S.-K. Tian, J. Org. Chem., 2009,
74, 9501-9504.
An iodine-catalyzed functionalization of various olefins and alkynes and direct
decarboxylative functionalization of cinnamic and propiolic acids with TosMIC
provides highy valuable vinyl, allyl, and β-iodo vinylsulfones. This simple,
efficient, and environmentally benign approach is attractive to both synthetic
and medicinal chemistry.
L. Kadari, R. K. Palakodety, L. P. Yallapragada, Org. Lett.,
2017, 19, 2580-2583.
A metal-free direct condensation of sodium arylsulfinates and β,β-disubstituted
nitroalkenes provides allylic sulfones in excellent yields with a broad
substrate scope under mild conditions. The key step of this process was a Lewis
base-promoted equilibrium between nitroalkenes and allylic nitro compounds,
which contain more reactive C=C bonds toward sulfonyl radical addition.
X. Lei, L. Zheng, C. Zhang, X. Shi, Y. Chen, J. Org. Chem., 2018, 83,
1772-1778.
Acetoxysulfones can serve as a novel class of chiral aldehyde equivalents
that are acid-stable but base-labile. The two functionalities impart good
diastereoselectivity in an electrophilic addition to the double bond. Thus, the
availability of the acetoxysulfones in high enantiopurity translates to an
asymmetric addition to one of the two enantiotopic faces of an α,β-unsaturated
aldehyde.
B. M. Trost, M. L. Crawley, C. B. Lee, J. Am. Chem. Soc., 2000,
122, 6120-6121.