(R,R)-1,2-(Methanesulfonamido)-cyclohexane

1a R = Me [122833-60-7] InChI = 1S/C8H12F6N2O4S2/c9-7(10,11)21(17,18)15-5-3-1-2-4-6(5)16-22(19,20)8(12,13)14/h5-6,15-16H,1-4H2/t5-,6-/m1/s1 InChIKey = GKSGSDYYIYURPD-PHDIDXHHSA-N 1b R = CF3 [290833-56-6] InChI = 1S/C14H30N2O4S2/c1-3-5-11-21(17,18)15-13-9-7-8-10-14(13)16-22(19,20)12-6-4-2/h13-16H,3-12H2,1-2H3/t13-,14-/m1/s1 InChIKey = JUGCCRUREILMAM-ZIAGYGMSSA-N 1c R = n-Bu [155237-72-2] InChI = 1S/C18H20N4O8S2/c23-21(24)13-5-9-15(10-6-13)31(27,28)19-17-3-1-2-4-18(17)20-32(29,30)16-11-7-14(8-12-16)22(25)26/h5-12,17-20H,1-4H2/t17-,18-/m1/s1 InChIKey = AHFPEDLBFJTANO-QZTJIDSGSA-N 1d R = 4-NO2Ph [166109-85-9] InChI = 1S/C12H26N2O4S2/c1-9(2)19(15,16)13-11-7-5-6-8-12(11)14-20(17,18)10(3)4/h9-14H,5-8H2,1-4H3/t11-,12-/m1/s1 InChIKey = WBVDMPSXIZEBDT-VXGBXAGGSA-N 1e R = i-Pr [263019-97-2] InChI = 1S/C24H34N2O4S2/c1-15-11-17(3)23(18(4)12-15)31(27,28)25-21-9-7-8-10-22(21)26-32(29,30)24-19(5)13-16(2)14-20(24)6/h11-14,21-22,25-26H,7-10H2,1-6H3/t21-,22-/m1/s1 InChIKey = IQJCBLZVBZRSFZ-FGZHOGPDSA-N 1f R = mesityl [122833-58-3] C8H18N2O4S2 (MW 270.36) InChI = 1S/C8H18N2O4S2/c1-15(11,12)9-7-5-3-4-6-8(7)10-16(2,13)14/h7-10H,3-6H2,1-2H3/t7-,8-/m1/s1 InChIKey = JUWLQVLCYRNWSV-HTQZYQBOSA-N (catalyst for organozinc-mediated additions to aldehydes,1 catalyst for Simmons–Smith type cyclopropanation of allylic alcohols2) Physical Data: mp 157 °C; [α]D20 −20.1 (c 3.07, pyridine). Solubility: soluble in most organic solvents except hydrocarbons. Form Supplied in: white solid. Preparative Methods: The enantiopure sulfonamide 1a is prepared via sulfonylation of (R,R)-1,2-diaminocyclohexane 2 in the presence of an excess of triethylamine (eq 1).3 Use of excess amine base is essential for obtaining a high yield of the bis-sulfonamide. Synthesis of related bis-sulfonamides is easily accomplished by substituting the desired sulfonyl chloride in the former procedure. Recrystallization of the bis-sulfonamide 1a from hexane/ethyl acetate and drying over P2O5 allows for isolation of the analytically pure reagent. Methanesulfonyl chloride and (R,R)-1,2-diaminocyclohexane 2 are commercially available from a number of sources. However it should be noted that racemic 1,2-diaminocyclohexane 2 can be resolved via formation of the tartrate salt.4 Typically, the diamine can be obtained in >99:1 enantiomeric ratio (er) after two crystallizations from water. Determination of the enantiopurity of the diamine is accomplished via formation of the bis-3-toluyl amide and analysis via chiral stationary phase HPLC (Chiralcel AD; hexane/i-PrOH; 95:5, 1.0 mL min−1). (1) Handling, Storage, and Precautions: The sulfonamide is a shelf-stable, non-hygroscopic compound which does not require special precautions for storage or handling.