.alpha.-Nitro sulfones. 2. Convenient new synthesis and selected functional group transformations

Abstract

X-ray Analysis of 2a. Single crystals of 2a were tetrahedral, space group P43 (for the configuration shown in Figure 1) or P4lt with a -12.896 (1) Á, c = 13.773 (3) A, and d^= 1.300 g cm"1 23 for Z = 4 (CggHgjjOg, mol wt 448.47). The intensity data were measured on a Hilger-Watts diffractometer (Ni-filtered Cu Ka radiation, 0-20 scans, pulse-height discrimination). A crystal measuring approximately 0.30 X 0.6 X 0.6 mm was used for data collection. A total of 1616 reflections was measured for 0 < 57°, of which 1570 were considered to be observed [/ > 2.5»(/)]. The structure was solved by a multiple solution procedure13 and was refined by full-matrix least-squares. In the final refinement (13)

Efficient 1,4-addition of α-substituted fluoro(phenylsulfonyl)methane derivatives to α,β-unsaturated compounds

“…Oxidation of (nitromethyl)(phenyl)sulfide with aqueous hydrogen peroxide [H 2 O 2 , 30% (wt)] was attempted in acetic acid at room temperature. Tuning the conditions by using 4-fold excess of H 2 O 2 afforded 90% yield of (nitromethylsulfonyl)benzene overnight ( Table 1 , entry 1) [ 26 – 28 ]. 2a – c and 2e were prepared in 76–91% yields under the optimized condition and used without further purification [ 30 – 34 ].…”

Synthesis of Enantiomerically‐Pure [13C]Aristeromycylcobalamin and Its Reactivity in Dioldehydratase, Glyceroldehydratase, Ethanolamine Ammonia‐Lyase and Methylmalonyl‐CoA Mutase Reactions

“…The anion formed from phenylsulphonylnitromethane (3) was most suitable for this purpose. Compound 3 was prepared by the method of Wade et al [20] but with major modifications (Scheme 2). As nitromethane is commercially available with a [ iodine and the base 1,8-diazobicyclo [5.4.0]undec-7-ene (DBU) to give phenylsulphonylnitromethane (3) in 40% yield.…”

Application of the AAA Reaction to the Synthesis of the Furanoside ofC-2-epi-Hygromycin A: A Total Synthesis ofC-2-epi-Hygromycin A

“…Benzoic (2 S ,5 S )‐5‐(1‐benzenesulfonyl‐1‐nitroethyl)‐2,5‐dihydrofuran‐2‐yl ester (12) : A solution of cis ‐2,5‐dibenzoxy‐2,5‐dihydrofuran ( 5 ; 2 g, 6.41 mmol), π‐allylpalladium chloride dimer (23 mg, 0.064 mmol, 1 mol %) and ( R , R )‐ 11 (178 mg, 0.26 mmol, 4 mol %) in dichloromethane (30 mL) were added to a sonicated, degassed solution of 1‐nitro‐1‐phenylsulfonylethane sodium salt 10 26 (1.922 g, 8.11 mmol) and tetra‐ n ‐hexylammonium bromide (0.28 g, 0.64 mmol) in water (30 mL). The reaction was vigorously stirred at room temperature for 16 h. The phases were separated, the organic layer dried over magnesium sulfate, filtrated and evaporated in vacuo.…”