Categories: C-S Bond Formation > Synthesis of sulfones >
Synthesis of benzylic sulfones
Recent Literature
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.
A palladium complex generated in situ from [Pd(η3-C3H5)Cl]2 and DPEphos
[bis(2-diphenylphosphinophenyl)ether] catalyzed the nucleophilic substitution of benzylic carbonates with sodium
arenesulfinates in DMSO at 80°C. The
reaction gave a variety of benzylic sulfones in
high yields.
R. Kuwano, Y. Kondo, T. Shirahama, Org. Lett., 2005, 7, 2973-2975.
Decatungstate photocatalysis enables a direct conversion of strong, aliphatic C(sp3)-H bonds into
the corresponding alkyl sulfinic acids . This
transformation has been applied to a diverse range of C(sp3)-rich scaffolds,
including natural products and approved pharmaceuticals, providing efficient
access to complex sulfur-containing products.
P. J. Sarver, N. B. Bissonnette, D. W. C. MacMillan, J. Am. Chem. Soc.,
2021, 143, 9737-9743.
Thiosulfonates synthesized by copper-catalyzed aerobic dimerization serve as
substrate for simple and high-yielding strategies for the production of a
variety of sulfones and sulfonamides. Thiosulfinates are stable, nontoxic
alternatives to metal sulfinate salts derived from toxic SO2.
P. K. Shyam, H.-Y. Jang, J. Org. Chem.,
2017, 82, 1761-1767.
Cyanide mediates an in situ generation of a nucleophilic sulfinate ion from
vinyl sulfones. Subsequent in situ S-alkylation provides sulfones in high
yields. In the presence of N-bromosuccinimide, primary and secondary amines
underwent sulfonamide formation.
T. Roy, J.-W. Lee, Synlett, 2020,
31,
455-458.
Sulfides/selenides and sulfones can be obtained simultaneously using a
nickel-catalyzed reductive coupling and SN2 synergistic reaction of
allyl/benzyl bromides with thiosulfonates/selenosulfonates. The strategy offers
excellent step economy, mild reaction conditions, broad functional group
compatibility, and excellent yields.
J.-M. Cao, W.-C. Zhu, X.-Y. Liu, W. Rao, S.-S. Shen, D.-p. Sheng, S.-Y. Wang, Org. Lett., 2023, 25,
9207-9212.
Treatment of methylarenes with 1,3-dibromo-5,5-dimethylhydantoin or N-bromosuccinimide
and a catalytic amount of 2,2′-azobis(isobutyronitrile) followed by a reaction
with a nucleophile, such as benzoic acid, p-toluenethiol, sodium p-toluenesulfinate,
aqueous dimethylamine, or succinimide, provides the corresponding benzylated
products in good yields.
H. Shimojo, K. Moriyama, H. Togo, Synthesis, 2015, 47,
1280-1290.
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.
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.
Related
Ni-catalyzed stereoconvergent Negishi arylations and alkenylations of
racemic α-bromosulfonamides and -sulfones furnish cross-coupling product in very
good ee and yield for an array of reaction partners. Mechanistic studies are
consistent with the generation of a radical intermediate.
J. Choi, P. Martín-Gago, G. C. Fu, J. Am. Chem. Soc., 2014,
136, 12161-12165.