Sulfur Dioxide Mediated One‐Pot, Four‐Component Synthesis of Polyfunctional Sulfones and Sulfonamides, Including Medium‐Ring Cyclic Derivatives.

Abstract

Multicomponent reactions O 0359Sulfur Dioxide Mediated One-Pot, Four-Component Synthesis of Polyfunctional Sulfones and Sulfonamides, Including Medium-Ring Cyclic Derivatives. -Further studies into the recently published multi-component synthesis of sulfones and sulfonamides are presented including application to the preparation of thiazonine and thiocine derivatives. In the oxyallylation of enoxysilanes the diastereoselectivity can be increased up to 9:1 depending on the nature of the reactands while the E/Z-selectivity is controlled by the amount of the acid promoter. -(BOUCHEZ, L. C.; TURKS, M.; DUBBAKA, S. R.; FONQUERNE, F.; CRAITA, C.; LACLEF, S.; VOGEL*, P.; Tetrahedron 61 (2005) 48, 11473-11487; Lab. Glycochem. Asymmetric Synth., Ec. Polytech. Fed. Lausanne, CH-1015 Lausanne, Switz.; Eng.) -Nuesgen 12-066

New Organic Chemistry of Sulfur Dioxide

“…Organosulfones and sulfonamides are important compounds because of their chemical and biological properties . Other electrophiles, EX, than MeI (e.g., allyl, methallyl, and arylmethyl bromides, BrCH 2 COOEt, alkyl iodides, and 2,4-dinitrofluorobenzene) combine with a large variety of 1-alkoxy- or 1-trialkylsilyloxy-1,3-diene 94 , SO 2 , and enoxysilanes or allylsilanes 95 , thus realizing a combinatorial, one-pot, four-component synthesis of polyfunctional sulfones 97 .…”

“…The reaction of 87c with diene (−)- 101 [97% enantiomeric excess (ee)] in SO 2 /toluene premixed with 0.3 equiv of Tf 2 NSiMe 3 at −78 °C gives a single silyl sulfinate 102 . Starting with (+)- 101 and 87c and by treatment of the intermediate silyl sulfinate ( ent - 102 ) with Pd(Ph 3 P), the 2 H -thiocene derivative (+)- 103 is obtained in 41% overall yield (Scheme ) …”

“…Organosulfones and sulfonamides are important compounds because of their chemical and biological properties. 59 Other electrophiles, EX, than MeI (e.g., allyl, methallyl, and arylmethyl bromides, BrCH 2 COOEt, 60 alkyl iodides, and 2,4-dinitrofluorobenzene) combine with a large variety of 1-alkoxy-or 1-trialkylsilyloxy-1,3diene 94, SO 2 , and enoxysilanes or allylsilanes 95, thus realizing a combinatorial, one-pot, four-component synthesis of polyfunctional sulfones 97. If the crude silyl sulfinates 96 are oxidized with Cl 2 or N-chlorosucciminide (NCS), the corresponding sulfonyl chlorides 98 are formed that can be reacted in situ with primary or secondary amines to generate polyfunctional sulfonamides 99 or with alcohols to give the corresponding sulfonic esters 100 (Scheme 15).…”