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Synthesis of allylic sulfones

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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.


The combination of Ph3P/ICH2CH2I promotes a dehydroxylative sulfonylation of benzylic and allylic alcohols with a variety of sulfinates in short reaction time. Using Ph2PMe and elevated temperatures, the protocol can be extended to alkyl alcohols. Various sulfonyl groups can be incorporated, such as CF3SO2 and HCF2SO2, which are fluorinated groups of interest in pharmaceutical chemistry.
Y.-J. Xiang, S.-Liu, J. Zhou, J.-H. Lin, X. Yao, J.-C. Xiao, J. Org. Chem., 2023, 88, 4818-4828.


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.


A highly regio- and enantioselective allylic sulfonylation of racemic branched allylic carbonates and Z and E linear allylic carbonates with readily available sulfonyl hydrazides provides branched allylic sulfones in very good yields with high regio- and enantioselectivities.
S. U. Rehman, C. Li, Org. Lett., 2023, 25, 3693-3697.


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.


A polyaniline-graphitic carbon nitride-titanium dioxide composite catalyzes a radical cascade reaction of an aryl diazonium salt, DABCO·(SO2)2 and 3-bromoprop-1-ene to provide aryl allyl sulfones under visible light irradiation. A series of substrates were tolerated, providing the corresponding products in good yields. Moreover, the photocatalyst could be readily recovered and reused several times.
L. Wang, L.-f. Zhang, Synlett, 2022, 33, 1929-1932.


A Pd-catalyzed multicomponent cross-coupling of allyl esters with alkyl bromides and K2S2O5 provides allylic sulfones with high linear and exclusive E selectivity. The reaction displays an excellent functional group compatibility.
K.-Y. Zhang, F. Long, C.-C. Peng, J.-H. Liu, L.-J. Wu, Org. Lett., 2023, 25, 5817-5821.


A direct allylic C-H bond activation of α-methylstyrene derivatives with sulfonylhydrazines provides allylic sulfones under exogenous oxidant- and metal-catalyst-free electrochemical conditions via radical coupling. A series of valuable allylic sulfones were accessed with a wide substrate scope and excellent regioselectivity.
X. Zhang, S. Xu, X. Yang, W. Pang, J. Org. Chem., 2023, 88, 7483-7488.


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.