Electronic Supplementary Material for PCCP This journal is The Owner Societies 2005 EXPERIMENTAL SECTION

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1 This journal is The wner Societies 00 EXPERIMETAL SECTI General Techniques: All reactions were carried out with dry, freshly distilled solvents under anhydrous conditions, unless otherwise stated. Tetrahydrofuran (TF) was distilled from sodium benzophenone, and methylene chloride (C) was distilled from calcium hydride. Acetonitrile was distilled over Ca and stored over Å molecular sieves. Yields refer to chromatographically and spectroscopically ( MR) homogeneous materials, unless otherwise stated. All reactions were monitored by thin layer chromatography (TLC) carried out on 0. mm E. Merck silica gel plates (0F ) using UV light ( nm). Merck silica gel (0 00 mesh) was used for flash chromatography. MR spectra were recorded on JEL JM-EX0 (0 Mz) or JEL Eclipse FT (00 Mz) instruments and calibrated using a solvent peak as an internal reference. The following abbreviations are used to indicate the multiplicities; s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad. Mass spectra were obtained using Agilent 00 via Electron Spray Ionisation geometry.ir spectra were recorded on a Perkin Elmer Spectrum ne spectrophotometer and only typical absorptions were cited. GEERAL PRCEDURE FR TE IMIE-FRMATI: To a stirred solution of indole--carbaldehyde ( equiv.) in C was added the respective amine ( equiv.) and MgS (0. equiv.). The reaction mixture was refluxed. After filtration of the MgS and evaporation of the solvent, the imine was obtained with good yield (9-9 %). If necessary, crystallisation in ethanol is possible. Compounds a, b have been described before in : P. Kumar, C. ath, K.P. Bhargava, K. Shanker, Indian Journal of Chem., 98, B, 8. A. Alemany, E. Fernandez Alvarez, J.M. Martinez-Lopez, Bull. Soc. Chim. France, 9, -,. Y. Shimoji, T. ashimoto, Y. Furukawa,. Yanagisawa, eterocycles, 99,,. a a -MR (0 Mz, CD, ppm): δ =.8 (, s, C (Ph)),.-. (0, m, C, C, C, C, C, x C(Ph)), 8. (, ~d, C=), 8. (, s, ); C-MR (8 Mz, CD, ppm): δ =. (C (Ph)),.8 (C ),.99 (C ),.9 (C ),. (C ),.0 (C a ),.0 (C ), 8.0 (x C(Ph)), 8.9 (C(Ph)), 8. (x C(Ph)), 9. (C quat (Ph)),.9 (C ), 0. (C a ),. (C=); IR (KBr, cm - ): (ν ); MS (0eV): m/z = (M + ); Mp.:. C. b a a -MR (00 Mz, CD, ppm): δ =.9 (, d, J =. z, x C (ipr)),.0 (, sept, J =. z, C(iPr)),.8-. (, m, C, C ),. (, ~d, J = 8. z, C or C ),. (, s, C ), 8.0 (, d, J =. z, C or C ), 8. (, s, (Ind)C=), not visible; C-MR (, Mz, CD, ppm):.8 (x C (ipr)),.90 (C(iPr)),. (C or C ),.9 (C ), 0.98 (C or C or C or C ),.0 (C or C or C or C ),.98 (C or C ),.90 (C a ),.8 (C ),.0 (C a ),.8 ((Ind)C=); IR (KBr, cm - ): 9 (ν C= ),,, 9, 8; MS (ESI): m/z = 8 (M + +); Mp.:. C.

2 This journal is The wner Societies 00 c (Et) P.0 C. a -MR (0 Mz, CD, ppm): δ =. (, t, J =. z, P()C C ),.0 (, d, J P =. z, C P),.8 (, m, P()C C ),.0 (, s, C ),.0 (, m, C, C ),. (, dd, J P =.8 z J =. z, C ), 8.09 (, d, J =. z, C ), 8. (, d, J =. z, C=), 0.00 (, s, ); C-MR (8 Mz, CD, ppm): δ =. (C, J CP =. z, P()C C ), 8. (J CP =.8 z, C P),.8 (C, J CP =. z, P()C C ),.8 (C ),.0 (d, J CP =. z C ),.0 (C ),.9 (C ),.8 (C ),.9 (C a ),.9 (C ),.8 (C a ), 0.9 (J CP =. z, C=); P-MR (09 Mz, CD, ppm): δ =.8; IR (KBr, cm - ): 0 (ν ), 9 (ν C= ); MS (0eV): m/z = 9 (M + ); Mp.: Preparation of d-g. To a stirred solution of indole--carbaldehyde (0.8 g, equiv.) in acetonitrile (0 ml) was added diëthyl amino(phenyl)methylphosphonate (0.98 g, equiv.) and 0. g (0. equiv.) MgS. The reaction mixture was refluxed for days. After filtration of the MgS and evaporation of the solvent, diëthyl (phenyl){[(e)--indole--ylmethylideen]amino} methylphosphonate was obtained with a yield of 98 %. Crystallisation in ethanol afforded yellow crystals with 8% yield. d a (Et) P -MR (0 Mz, CD, ppm): δ =.9 (, t, J =. z, P()C C ),. (, t, J =.9 z, P()C C ),.09 (, m, P()C C ),.8 (, d, J P =.8 z, CP),.09 (, s, C ),.-. (, m, C, C, C, C (Ph), C (Ph), C (Ph)),.8 (, d, J =.9 z, C (Ph), C (Ph)), 8. (, d, J =. z, C=), 8. (, d, J =. z, C ), 0.0 (, s, ); C-MR (8 Mz, CD, ppm): δ =. (C, J CP =.9 z, P()C C ),. (J CP =. z, P()C C ),. (J CP =. z, P()C C ),.8 (J CP =. z, CP),.9 (C ),. (C ),. (C ),.9 (C ),.8 (C ),.8 (C a ),. (J CP =. z, C(Ph)), 8. (C, J CP =.9 z, C(Ph)), 8. (C, J CP =.9 z, C(Ph)),.8 (C ),. (d, J CP =. z, C quat (Ph)),. (C a ), 9. (J CP =.8 z, C=); P-MR (09 Mz, CD, ppm): δ =.9; IR (KBr, cm - ): 0 (ν ), 9 (ν C= ); MS (0eV): m/z = (M + ); Mp.: 0. C. e a (Et) P F -MR (0 Mz, CD, ppm): δ =. (, t, J =.9 z, P()C C ),. (, t, J =. z, P()C C ),. (, m, P()C C ),.8 (, d, J P =. z, CP),.0 (, m, C, x C(Ph)),. (, m, C, C ),. (, dd, J =. z, J =.8 z, C ),. (, m, x C(Ph)), 8. (, d, J P =. z, C=), 8. (, dd, J =. z, J =.8 z, C ), 0. (, s, ); C-MR (8 Mz, CD, ppm): δ =.8 (C, J CP =. z, P()C C ),.09 (J CP =. z, P()C C ),.0 (J CP =. z, P()C C ),.0 (J CP =. z, CP),.88 (C ),. (J CP =. z, C ),. (C, d, J CF =. z, C(Ph)),.0 (C ),.90 (C ),.98 (C ),.8 (C a ), 9.88 (C, t, J CF =. z, C(Ph)),. (C ),. (dd, J =. z, J =. z, C quat (Ph)),. (C a ), 9. (J CP =.9 z, C=),. (dd, J CF =. z, J CP =. z, CF), P-MR (09 Mz, CD, ppm): δ = 0.; IR (KBr, cm - ): 8 (ν ), 9 (ν C= ); MS (0eV): m/z = 88 (M + ); Mp.:.8 C.

3 This journal is The wner Societies 00 f -MR (0 Mz, CD, ppm): δ =.8 (, t, J =. z, P()C C ),. (, t, J =. z, P()C C ),. (, m, P()C C ),. (, d, J P = 8. z, CP),.0 (, s, C ),. (, m, C, C ),.9 (, m, C, x C(Ph)), 8. (, d, J =. z, C=), 8. (, m, C ), 0.0 (, s, ); C- MR (8 Mz, CD, ppm): δ =.8 (C, t, J CP =. z, P()C C ),. (J CP = 8. z, P()C C ),.08 (J CP =. z, P()C C ),.8 (J CP =.8 z, CP),.88 (C ),. (J CP =. z, C ),. (C ),.0 (d, J CP =.9 z, CBr),.9 (C ),.0 (C ),. (C a ), 0.00 (C, J CP =.9 z, C(Ph)),. (C, J CP =. z, C(Ph)),. (C ),. (d, J = 8. z, C quat (Ph)),. (C a ), 9. (J CP =.9 z, C=); P-MR (09 Mz, CD, ppm): δ = 0.; IR (KBr, cm - ):. C. g (ν ), (ν C= ); MS (0eV): m/z = /9 (M + ); Mp.: -MR (0 Mz, CD, ppm): δ =.9 (, t, J =.8 z, P()C C ),. (, t, J =. z, P()C C ),.80 (, s, C ),.9 (, m, P()C C ),.8 (, d, J P =. z, CP),.9 (, d, J = 8. z, C(Ph)),.0 (, s, C ),. (, m, C, C ),. (, C ),. (, m, C(Ph)), 8. (, t, J =. z, C=), 8. (, m, C ), 0. (, s, ); C-MR (8 Mz, CD, ppm): δ =. (C, P()C C ),. (C ). (J CP =. z, P()C C ),.9 (J CP =.8 z, P()C C ),.8 (J CP =.0 z, CP),.00 (C ),.8 (C, C(Ph)),.8 (C ),. (C ),.0 (C ),.0 (C ),. (C a ), 9. (C a ), 9. (CMe), 9. (J CP =. z, C=); P-MR (09 Mz, CD, ppm): δ =.90; IR (KBr, cm - ): 8 (ν ), 9 (ν P= ); MS (0eV): m/z = 0. (M + ); Mp.:. C. Summary a (Et) P a (Et) P Br Me Compound Reaction Yield (%) Compound Reaction Yield (%) Time (hours) Time(days) a 0 9 d 8 b 8 88 e 8 c f g 88

4 This journal is The wner Societies 00 GEERAL PRCEDURE FR TE AMIE-FRMATI: The imine from the previous section was dissolved in absolute ethanol and equiv. ab was added. After stirring at room temperature h, the mixture was quenched by the addition of 0. M a and stirred for 0 minutes. ext, the mixture was poured in dichloromethane and washed three times with 0. M a. After filtration of the MgS and evaporation of the solvent, the amine was obtained in good yields. a a -MR (0 Mz, CD, ppm): δ =.80 (, bs, ),.8 (, s, (C (Ph)),.00 (, s, (Ind)C ),.0 (, s, C ),.-. (8, m, C, C, C, x C(Ph)),. (, d, J =. z, C ), 8. (, bs, (ind)); C-MR (8 Mz, CD, ppm): δ =. (C (Ph)),. ((Ind)C ),. (C ),.9 (C ), 8.9 (C ), 9. (C ),. (C ),. (C ),. (C a ), 8. (C(Ph)), 8. (C, x C(Ph)), 8. (C, x C(Ph)),. (C a ), 0. (C quat (Ph)); IR (KBr, cm - ): (ν ); MS (0eV): m/z = (M + ); Mp.:. C. b a a -MR (00 Mz, CD, ppm):. (, d, J =, z, x C (ipr)),.8 (, bs, ),.9 (, sept, J =. z, C(iPr)),.98 (, s, (Ind)C ),.9 (, s, C ),. (, dxd, J = J =. z, C or C ),. z (, ~t, J = J =. z, C or C ),. (, d, J = 8. z, C or C ),. (, d, J =. z, C or C ), 8.98 (, bs, (Ind)); C-MR (. Mz, CD, ppm):.8 (x C (ipr)),. ((Ind)C ), 8.8 (C(iPr)),. (C or C ),.0 (C ), 8. (C or C ), 9.9 (C or C ),.8 (C or C ),.0 (C ),.9 (C a or C a ),. (C a or C a ); IR (a, cm-): (ν ),, 0; MS (ESI): m/z = 90 (M++), (Ind-C + +). c (Et) P a -MR (0 Mz, CD, ppm): δ =.9 (, t, J =.9 z, P()C C ),. (, s, ),.0 (, d, J P =. z, C P),. (, m, P()C C, (Ind)C ),.0 (, d, J =.0 z, C ),. (, m, C, C ),. (, d,.9 z, C ),. (, d, J =.9 z, C ), 8.9 (, s, (Ind)); C-MR (8 Mz, CD, ppm): δ =. (C, J CP =.9 z, P()C C ),.8 (J CP =.8 z, C P),.8 (J CP =.9 z, (Ind)C ),. (C, J CP =. z, P()C C ),. (C ),.9 (C ), 8. (C ), 9. (C ),.9 (C ),.0 (C ),.9 (C a ),. (C a ), P-MR (09 Mz, CD, ppm): δ =.8; IR (a, cm - ): (ν P= ), (ν ) ; MS (0eV): m/z = (M + ). Preparation of d-g. To a stirred solution of diëthyl (phenyl){[(e)--indole--ylmethylideen] amino} methylphosphonate d in ethanol (0 ml) was added at 0 C 0. g (. equiv.) ab. After days at room temperature the reaction mixture was quenched with 0 ml of 0. M a. The reaction mixture was poured in C (0 ml).the organic phase was washed three times with 0 ml 0. M a and dried over anhydrous MgS. After filtration and evaporation of the solvent the crude residue was further purified by flash chromatography (EtAc/PE/triethylamine: 89/0/, Rf= 0.0, yield= %).

5 This journal is The wner Societies 00 d a (Et) P -MR (00 Mz, CD, ppm): δ =. (, t, J =.0 z, P()C C ),. (, t, J =.0 z, P()C C ),. (, s, ),. (, d, J AB =. z, (Ind)C ),.98 (, m, P()C C ),.0 (, d, J AB =. z, (Ind)C ),. (, d, J P = 9.8 z, CP),.9 (, d, J =. z, C ),.0 (, dxdxd, J = J =. z, J =.0 z, C ),. (, dxdxd, J = J =. z, J =. z, C ),.8 (, m, C, x C(Ph)),. (, m, x C(Ph)),. (, d,. z, C ), 9.9 (, s, (Ind)); C-MR (. Mz, CD, ppm): δ =. (J CP =. z, P()C C ),. (J CP =. z, P()C C ),. (J CP = 8. z, (Ind)C ), 9. (J CP =. z, CP),.98 (J CP =. z, P()C C ),.0 (J CP =.9 z, P()C C ),. (C ),. (C ), 9.00 (C ), 9. (C ),.8 (C ),. (C ),. (C a ), 8.08 (C (Ph)), 8. (C (Ph), C (Ph)), 8.9 (C, J CP =. z, C (Ph), C (Ph)),.9 (C a ),.9 (C (Ph)); P-MR (. Mz, CD, ppm): δ =.; IR (a, cm - ): 09 (ν ), 9 (ν ), 0 (ν P= ); MS (0eV): m/z = (M + ). e a (Et) P F -MR (0 Mz, CD, ppm): δ =. (, t, J =.0 z, P()C C ),. (, t, J =.0 z, P()C C ),. (, s, ),. (, d, J AB =. z, (Ind)C ),.0 (, m, P()C C ),.0 (, d, J AB =. z, (Ind)C ),. (, d, J P = 9. z, CP),.9 (, d, J =. z, C ),.0 (, m, x C(Ph), C ),. (, dxd, J = J =.0 z, C ),. (, d, J = 8, z, C ),. (, m, C(Ph)),.8 (, d, J =. z, C ), 8.9 (, s, (Ind)); C-MR (. Mz, CD, ppm): δ =. (C, t, J CP =.8 z, P()C C ),. (J CP =.9 z, (Ind)C ), 8.9 (J CP =.0 z, CP),.9 (J CP =. z, P()C C ),. (J CP =. z, P()C C ),.0 (C ),. (C ),.0 (C, d, J CF = 0.8 z, C(Ph)), 0. (x C(Ph)),. (C a ),.9 (C q (Ph)),. (d, J CP =. z, CF); P-MR (09 Mz, CD, ppm): δ =.; IR (KBr, cm - ): (ν P= ), (ν ); MS (0eV): m/z = 9 (M + ), Rf (ethylacetate) = 0.0. f a (Et) P Br -MR (0 Mz, CD, ppm): δ =. (, t, J =. z, P()C C ),. (, t, J =. z, P()C C ),. (, s, ),. (, d, J AB =. z, (Ind)C ),.9 (, m, P()C C ),.99 (, d, J AB =. z, (Ind)C ),. (, d, J P = 9.8 z, CP),.9 (, d, J =.9 z, C ),.09 (, dxd, J = J =. z, C ),.8 (, dxd, J = J =. z, C ),.0 (, m, C x C(Ph)),.8 (, d, J =. z, C ), 8. (, s, (Ind)); C-MR (8 Mz, CD, ppm): δ =. (C, t, J CP =. z, P()C C ),. (J CP =.9 z, (Ind)C ), 9. (J CP =.9 z, CP),.00 (J CP =.9 z, P()C C ),.8 (J CP =. z, P()C C ),. (C ),. (C ), 9.0 (C ), 9. (C ),.9 (CBr),. (C ),. (C ),.0 (C a ), 0. (d, J CP =. z, x C(Ph)),.8 (x C(Ph)),. (C a ),. (C q (Ph)); P-MR (09 Mz, CD, ppm): δ =.; IR (KBr, cm - ): (ν P= ), (ν ); MS (0eV): m/z = (M + ), Rf (ethylacetate/petrolether 9/) = 0.0.

6 This journal is The wner Societies 00 g -MR (0 Mz, CD, ppm): δ =. (, t, J =. z, P()C C ),. (, t, J =. z, P()C C ),. (, s, ),. (, d, J AB =. z, (Ind)C ),.8 (, s, C ),.00 (, d, J AB =. z, (Ind)C ),.0 (, m, P()C C ),.0 (, d, J P = 9. z, CP),.9 (, d, J = 8. z, C(Ph)),.9 (, d, J =. z, C ),.08 (, dxdxd, J = J =. z, J =. z, C ),.8 (, dxdxd, J = J =. z, J =. z C ),. (, d, J = 8.0 z, C ),.9 (, dd, J P = 8.8 z, J =. z, x C(Ph)),.9 (, d, J = 8.0 z, C ), 8.80 (, s, (Ind)); C-MR (8 Mz, CD, ppm): δ =.8 (d, J CP =.8 z, P()C C ),. (d, J CP =.8 z, P()C C ),. (J CP = 8. z, (Ind)C ),. (C ), 8.99 (J CP =. z, CP),.8 (J CP =.9 z, P()C C ),.0 (J CP =. z, P()C C ),. (C ),. (C ),.00 (x C(Ph)), 9.08 (C ), 9. (C ),.98 (C ),. (C ),. (C a ),. (C q (Ph)), 9.9 (C, J CP =.8 z, x C(Ph)),. (C a ), 9.0 (C(Ph)Me); P-MR (09 Mz, CD, ppm): δ =.9; IR (a, cm - ): 8 (ν P= ), (ν ); MS (0eV): m/z = 0 (M + ), Rf (ethyl acetate/petrolether /) = 0.. Summary a (Et) P Me Compound Yield (%) Compound Yield (%) a 9 d b 9 e c 80 f g

7 This journal is The wner Societies 00 GEERAL PRCEDURE FR TE ACYLATI: To a stirred solution of the respective amine and equiv. of pyridine, equiv. trichloroacetyl chloride was added dropwise at 0 C and under nitrogen atmosphere. The reaction mixture was carefully protected from the light and stirred for to 8 h at room temperature under a nitrogen atmosphere. The reaction mixture was poured in M a and extracted three times with C. The combined organic fractions were dried over MgS. The crude mixture was further purified through filtration over a small ( cm) silica column using petroleumether/ ethyl acetate. Because of the photo lability of the compound, it is important to protect the compound as much as possible from the light. The spectrum shows the existance of rotamers. The mixture consist of % rotamer A and % rotamer B. -MR (00 Mz, CD, ppm): δ =. (, s, C (Ph), rot B),. (, s, (Ind)C, rot A),.8 (, s, C (Ph), rot A),.08 (, s, (Ind)C, rot B),.0 (, s, C, rot A),.0 (, s, C, rot B), a.-.0 (8 (rot A), 8 (rot B), m, C, C, C or C, x C(Ph), rot A, rot B),.0 (, ~d, J =. z, C or C, rot A, rot B), 8. (, bs,, rot A), 8.8 (, bs,, rot B); a C-MR (. Mz, CD, ppm): δ =. ((Ind)C, rot A),. ((Ind)C, rot B), 0.0 (C (Ph)), rot B),. (C (Ph)), rot A), 9.8 (C, rot A, rot B), 0.0 (C, rot B), 0.0 (C, rot A),. (C or C, rot A),.8 (C or C, rot B), 9.09 (C or C, rot B), 9.0 (C or C, rot A), 0. (C or C, rot A, rot B),.9 (C or C, rot A, rot B),. (C, rot B),.0 (C, rot A),.0 (C a ),. (C, x C(Ph)),.98 (C, x C(Ph)), 9.0 (C(Ph)),. (C quat(ph), rot A, rot B),. (C a, rot A),. (C a, rot B),. (C=, rot A, rot B); IR (KBr, cm - ): 0(ν ), (ν C= ), 9,, ; MS (ESI): m/z = 0 (Ind-C + ); Mp.:. C. b a a C -MR (00 Mz, CD, ppm):. (, d, J =. z, x C (ipr)),. (, s, (Ind)C ), (, m, C(iPr)),.-. (, m, C, C, C ),. (, d, J =. z, C or C ),. (, d, J = 8. z, C or C ), 8.09 (, bs, (Ind)); C-MR (. Mz, CD, ppm): 0. (x C (ipr)), 8.0 ((Ind)C ), 0.8 (C(iPr)), 9.99 (C ),.8 (C or C ),. (C ), 8.8 (C or C ), 9.,.99,. (C, C, C ),.8 (C a or C a ),. (C a or C a ), 0. (C=); IR (KBr, cm-): 9 (ν ), (ν C= ); MS (ESI): m/z = (Ind-C + +); Mp.:.8 C. c a (Et) P C -MR (0 Mz, CD, ppm): δ =. (, t, J =. z, P()C C ),. (, t, J =.9 z, P()C C ),.8 (, d, J P =. z, C P),. (, m, P()C C ),. (, s, (Ind)C ),. (, dxd, J = J =. z, C ),. (, m, C, C ),. (, d, J =.9 z, C ),. (, d, J =.9 z, C ), 9.0 (, s, (Ind)); C-MR (8 Mz, CD, ppm): δ =. (C, J CP =. z, P()C C ),.8 (J CP =.0 z, C P),.90 ((Ind)C ),. (C, J CP =. z, P()C C ), 9.0 (C ), 08.8 (C ),.8 (C ), 8.8 (C ), 0. (C ),. (C ),. (C ),. (C a ),. (C a ), 0. (C=); P-MR (09 Mz, CD, ppm): δ =.00; IR (a, cm - ): (ν P= ), (ν ), (ν C= ), ; MS (0eV): m/z = 0. (Ind-C + ).

8 This journal is The wner Societies 00 Preparation of d. To a stirred solution of 0. g diëthyl (phenyl)[(-indole--ylmethyl)amino]methylphosphonate d and pyridine (0.8 g, equiv.) in 0 ml TF, was added trichloroacetyl chloride (0. g, equiv.) dropwise at 0 C and under a nitrogen atmosphere. The reaction mixture was carefully protected from the light and stirred for exactly hours at room temperature under a nitrogen atmosphere. An excess of Et was added to the reaction mixture and stirred for 0 minutes at 0 C. The salts were filtered over celite and washed with Et. The organic layer was washed three times with water (0 ml), dried over MgS, filtered, and concentrated under reduced pressure to afford ( %) as a bright yellow oil. The residue has a purity > 9 %. Because of the photo lability it is important to protect the reaction mixture as much as possible from the light. -MR (00 Mz, CD, ppm):.08 (, t, J =.0 z, (Et) P P()C C ),.0 (, t, J =. z, P()C C ),.-.90 (, m, P()C C ),. (, q, J =. z, P()C C ),. (, d, J AB =. z, (Ind)C ),.89 (, d, J -P =. z, CP),.8 C a (, dxd, J AB =. z, J =. z, (Ind)C ),.0 (, dxd, J = J =. z, C or C ),.0 (, dxd, J = J =. z, C or C ),.-.9 (, m, x C(Ph)),. (, ~ t, C, C ),.9 (, s, d C ), 9. (, bs, (ind)); C-MR (. Mz, CD, ppm): δ =. (J CP =.9 z, P()C C ),.8 (J CP =.8 z, P()C C ),.8 ((Ind)C ),. (J CP =. z, P()C C ),),.8 (J CP = 9. z, CP),. (J CP =. z, P()C C ), 9.0 (C ), 08.9 (C ),.9 (C or C ), 8.0 (C or C ), 9.0 (C or C ),. (C or C ),. (C ),.8 (C a ), 8.9 (C(Ph)), 8. (C(Ph)), 8. (C(Ph)), 8.8 (C, x C(Ph)),. (C quat (Ph)),. (C a ),. (C=); P-MR (. Mz, CD, ppm): δ = 0.; IR (a, cm - ): (ν ), 90, 8(ν C= ), (ν P= ), 09 (ν P- ); MS (ESI): m/z = 0 (Ind-C + ). Summary Compound Reaction Yield (%) Time (hours) a 8-9 b c 8 d 8

9 This journal is The wner Societies 00 GEERAL PRCEDURE FR TE ALGE TRASFER RADICAL CYCLIZATI: A mixture of the trichloroacetyl amino-derivative ( equiv.) and TMEDA (0.8 equiv.) was dissolved in C and flushed with argon for minutes. Cu(I) (0. equiv.) was added and the reaction mixture was stirred for hours at room temperature under argon atmosphere and finally quenched with water and stirred for 0 minutes. The organic phase was washed with water until the blue colour of the wash water disappeared. After drying over MgS, filtration and evaporation of the solvent, the spiro compound was obtained. By adding chloroform/diethylether or ethanol it was sometimes possible to obtain the compount as an amorf (more pure) precipitate. -MR (00 Mz, CD, ppm): δ =. (, d, J AB = 0. z, (Ind)C ),.9 (, d, J AB = 0. z, (Ind)C ),.9 (, d, J AB =. z, C (Ph)),. (, d, J AB =. z, C (Ph)),.0-. (8, m, C, C, C or C, x C Ph)),. (, dxd, J = 8. z, J =. z, C or C ),.98 (, s, C ); C-MR (. Mz, CD, ppm): δ = 8.09 a ((Ind)C ), 8.8 (C (Ph)),. (C ), 8. (C ),. (C or C ), {.,., 8., 0. (C, C, C(Ph), C or C )}, 0a 8. (C, x C(Ph)), 9. (C, x C(Ph)),. (C a ),. (C quat, (Ph)),. (C a ),.8 (C=), 9.0 (C ); IR (a, cm - ): 9(ν =C(Ind) ), (ν C= ), 8,, 8; MS (ESI): m/z = //9 (M+ + ). -MR (00 Mz, CD, ppm):. (, d, J =. z, C (ipr)),. (, d, J =. z, C (ipr)),. (, d, J AB = 9.9 z, (Ind)C )),. (, d, J AB = 0. z, (Ind)C )),. (, sept, J =. z, C(iPr)),. (, dxdxd, J = J =. z, J = 0.8 z, C or C ),.0 (, dxdxd, J = J =. z, J =. z, C or a C ),. (, d, J =. z, C or C ),.0 (, d, J =. z, C or C ), 8. (, s, C ); C-MR (. Mz, CD, ppm): 9. (C (ipr)), 9. (C (ipr)),.0 ((Ind)C ),.9 (C(iPr)),.8 (C ), 8.9 (C ),.8 0b (C or C ),.9 (C or C ),. (C or C ), 0. (C or C ),.0 (C a ),. (C a ),.8 (C=), 9.0 (C ); IR (a, cm - ): (ν =C(Ind) ), (ν C= ); MS (ESI): m/z = 9/99/0 (M + +). -MR (00 Mz, CD, ppm):. (, t, J =.9 z, P()C C ), (Et) P. (, t, J =.0 z, P()C C ),.8 (, s, (Ind)C ),.8 (, dd, J P =.8 z, J =. z, C P),.9 (, dd, J P =.8 z, J =. z, C P),. (, m, P()C C ),. (, dxd, J =J =. z, a C ),.8 (, dxdxd, J = J =. z, J =. z, C ),.8 (, d, J =. z, C ),.8 (, d, J =. z, C ), 8. (, s, C ); C-MR (8 0c Mz, CD, ppm): δ =. (J CP =. z, P()C C ),.8 (J CP =. z, P()C C ), 9.8 (J CP =.8 z, C P), 9. ((Ind)C ),.0 (J CP =. z, P()C C ),. (J CP =. z, P()C C ), 8.0 (C ), 8. (C ),. (C ),.8 (C ),. (C ), 0. (C ),. (C a ),.89 (C a ),. (C=), 8.8 (C ); P-MR (09 Mz, CD, ppm): δ = 9.8; IR (a, cm - ): (ν P= ), (ν C= ), (ν ); MS (0eV): m/z = 09. 9

10 This journal is The wner Societies 00 -MR (00 Mz, CD, ppm):.-. (, m, P()C C ),.9 (, ~t, (Ind)C ),.9-. (, m, (Ind)C, P()C C ),.9 (, d, J P = 0. z, CP, m),.80 (, d, J -P = 0.9 z, CP, M), (Et) P.-. (9, C, C, C, C, x C(Ph)), 8. (, s, C, M), 8.8 (, ~dxd, C, m); C-MR (. Mz, CD, ppm):.8 (J CP =.8 z, P()C C ),.9 (J CP =.9 z, P()C C ),. ((Ind)C, a m),.90 ((Ind)C, M),.9 (J CP = 8. z, CP),.98 (J CP =.9 z, P()C C, M ),.0 (J CP =.9 z, P()C C, m ),.9 (J CP =.9 0d z, P()C C, M),.0 (J CP =.9 z, P()C C, m),.9 (C ), 8. (C ), {.99,.0,.9, 0.9 (C, C, C and C )}, 9. (C, x C(Ph)), 9.8 (C, x C(Ph)), 9.89 (C(Ph)),.8 (C a or C quat (Ph)),.9 (C a or C quat (Ph)),.80 (C a ),. (C=), 8.8 (C, m), 8.9 (C, M); P-MR (. Mz, CD, ppm): δ = 8. (M), 8.0 (m); IR (a, cm - ): 80(ν ), 98, (ν C= ), (ν P= ), 09 (ν P- ) ; MS (ESI): m/z = 80/8/8 (M+ + ),. Compound Yield (%) Purity (%) 0a 9 8 0b c 9 8 0d 8 GEERAL PRCEDURE FR TE REDUCTI F TE SPIR-IMIE: To a mixture of the previous spiro-imine 0 and. equiv. of glacial acetic acid in methanol was added equiv. of acb. The reaction mixture was stirred for h at room temperature, poured in 0. M a and extracted three times with dichloromethane. After drying over MgS the compound was obtained with moderate purity. a a -MR (00 Mz, CD, ppm): δ =. (, d, J AB = 9.8 z, C ),.0 (, d, J AB = 9.8 z, C ),. (, d, J AB = 0. z, (Ind)C ),.80 (, bs, ),.09 (, d, J AB = 0. z, (Ind)C ),.9 (, d, J AB =. z, C (Ph)),.8 (, d, J AB =. z, C (Ph)),.-.9 (, m, C, C ),.9 (, dxd, J =.8 z, J =. z, C ),. (, dxdxd, J = J =. z, J =.z, C ),.-. (, m, x C(Ph)); C-MR (. Mz, CD, ppm): δ = 8. (C (Ph)),. ((Ind)C ),.0 (C ), 9. (C ), (C ), 0.8 (C ), 9.0 (C ),.80 (C ), 8.9 (C a ), 8. (C(Ph)), 8.8 (C, x C(Ph)), 9. (C, x C(Ph)), 0.0 (C ),.8 (C quat, (Ph)),.9 (C a ),. (C=); IR (a, cm - ): 8(ν ), 0 (ν C= ), 8,, 8; MS (ESI): m/z = /9/ (M+ + ). 0

11 This journal is The wner Societies 00 c (Et) P a -MR (0 Mz, CD, ppm):. (, t, J =.0 z, P()C C ),. (, t, J =. z, P()C C ),.8 (, d, J = 0. z, (Ind)C ),.8 (, dd, J P =. z, J = 0.9 z, C P),.9 (, d, J = 0.0 z, C ),.8 (, d, J = 0. z, C ),.9 (, dd, J P =.0 z, J =. z, C P),.0 (,dt, J = 0. z, (Ind)C ),. (, m, P()C C ),.8 (, m, C, C ),.98 (, dxd, J = 8.0 z, J =. z, C ),. (, dxdxd, J = J =. z, J =. z, C ); C-MR (8 Mz, CD, ppm): δ =. (J CP =.8 z, P()C C ),. (J CP =.8 z, P()C C ), 9.0 (J CP =. z, C P),. ((Ind)C ),. (C ), 9.8 (C ),.8 (J CP =. z, P()C C ),.0 (J CP =.8 z, P()C C ), 8.90 (C ), 0. (C ), 9.0 (C ),.99 (C ), 8. (C a ), 0.0 (C ),. (C a ),.8(C=); P-MR (09 Mz, CD, ppm): δ = 0.; IR (a, cm - ): 0 (ν C= ), (ν ); MS (0eV): m/z =. Compound Yield (%) Purity (%) a 88 c 90 Procedure for the synthesis of the Boc-derivate g (. mmol) of a was dissolved together with. g (.9 mmol,. equiv.) Boc and 0.0 g (0. mmol, 0. equiv.) DMAP in acetonitrile. The reaction was stirred for h at room temperature. The solvent was then concentrated in vacuo and the mixture was again dissolved in C. The organic layer was washed times with M a. After drying over MgS and evaporating the solvent, the crude mixture was further purified through filtration over a small silica column ( cm) with ethylacetate/petroleum ether (/) as solvent. The compound was obtained as a yellow powder (9 %). The spectrum shows the existance of rotamers. -MR (00 Mz, CD, ppm): δ =. (9, bs, C(C ) ),. (, bs, (Ind)C ),.9 (,~ d, C (Ph)),.-. (9, m, C, C or C, C, C, x C(Ph)), 8. (, d, J =.9 z, (C or a C ); C-MR (. Mz, CD, ppm): δ = 8.08 (C, C(C ) ), C.8 ((Ind)C ),. (C (Ph)), 8. (CC ), 9. (C ), xx. (C ),. (C or C ), 9.9 (C or C ), {.8,.,.,.0,.8, 8.8,.99,. (C, C, C, C a, C a, x C(Ph), x C(Ph), C(Ph))}, 9.8 (C=()), 0.8 (C=(C )) The signal of C quat (Ph) coincide with an other peak; IR (KBr, cm - ):, (ν C=() ), (ν C=(C) ),,,, 088; MS (0eV): m/z =00, 0 (Ind-C + ), 0 (Boc-Ind-C + ), 0; Mp.:. C. Procedure for the synthesis of -[(-methylphenyl)sulfonyl]--indole--carbaldehyde To a solution of 0 g (8.8 mmol) indole--carbaldehyde in TF was added at 0 C.8 g (. mmol,. equiv) a. The reaction mixture was stirred for h at room temperature. ext. g (8.8 mmol, equiv.) tosylchloride was added and the mixture was stirred for h at room temperature. The mixture was quenched with an excess of water. Carefully stirring for minutes afforded rose crystals. These crystals werd filtrated and washed three times with 0.M cold a. After drying at high vacuum the compound was obtained with a yield of 8 %. If necessary recrystallisation is possible in TF/water.

12 This journal is The wner Societies 00 xx -MR (00 Mz, CD, ppm):.8 (, s, C ),.-.8 (, m, C (Ts), C (Ts), C, C ),.8-.8 (, m, C (Ts), C (Ts)),.9-.9 (, m, C or C ), 8. (, s, C ), (, m, C or C ), 0.0 (, s, (C=)); C-MR (. Mz, CD, ppm): δ =. (C ),. (C or C ),. (C or C a or C a ),.9 (C or C ),. (C or C ),. (C or C ),. (C, C (Ts), C (Ts)), 0. (C, C (Ts), C (Ts)),. (C or C a or C a ),. (C or C a or C a ),.(C ),.8 (C quat (Ts)), 8.9 ((C=)), the signal C quat (Ts) coincide with an other peak; IR (KBr, cm - ): (ν C=() ), 9,,, (ν S ); MS (ESI): m/z = 00(M+ + ); Mp.: 0. C. Procedure for the synthesis of -benzyl-{-[(-methylfenyl)sulfonyl]--indole-yl} metanamine via reductive amination. The imine obtained according the general procedure was immediately reduced according the general procudere for reduction. Crystallisation in ethanol/0. M a afforded yellow crystals in % yield. -MR (00 Mz, CD, ppm):. (, bs, ),. (, s, C ),.9 (, s, C (Ph)),.8 (, s, (Ind)C ),. (, d, J = 8.0 z, C (Ts), C (Ts)),.8-. (, m, C, C, x C(Ph)),.9 (, s, C ),. (, d, J =. z, C or C ),. (, d, J = xx. z, C (Ts), C (Ts)),.99 (, d, J = 8. z, C or C ); C-MR (. Mz, CD, ppm): δ =. (C ),.9 ((Ind)C ),.9 (C (Ph)),.88 (C or C ), 9.99 (C or C ),. (C ),.8 (C or C ),.89 (C ),.9 (C or C ),.9 (C, C (Ts), C (Ts)),. (C(Ph)), 8. (C, x C(Ph)), 8.0 (C, x C(Ph)), 9.9 (C, C (Ts), C (Ts)), 0. (C a or C a or C quat(ts)),.8 C a or C a or C quat(ts)),. (C a or C a or C quat(ts)), 0. (C quat(ph)),.98 (C quat(ts)); IR (KBr, cm - ): (ν ), 9, 9,, (ν S ); MS (ESI): m/z = 8 (Ts-Ind-C + ); Mp.: 9. C. The acylation was performed according the previous general procedure. Reaction time h, yield: %. The spectrum shows the existance of rotamers. The mixture consist of % rotamer A and % rotamer B. -MR (00 Mz, CD, ppm): δ =. (, s, C, rot A, rot B),. (, s, C (Ph), rot B),.9 (, s, (Ind)C, rot a a a a S a a S C S a A),.8 (, s, C (Ph), rot A),.9 (, s, (Ind)C, rot B),.08-. (, m, C, C or C, C, C, x C(Ph), {C (Ts), C (Ts) or C (Ts), C (Ts)}, rot A, rot B),. (, d, J = 8. z, C (Ts), C (Ts) or C (Ts), C (Ts), rot A, rot B), 8.0 (, d, J = 8.0 z, C or C, rot A, rot B); C-MR (. Mz, CD, ppm): δ =. (C, rot A, rot B),. ((Ind)C, rot A),. ((Ind)C, rot B), 0. (C (Ph)), rot B),.8 (C (Ph)), rot A), 9. (C, rot A, rot B),.8 (C or C, rot A),.9 (C or C, rot B),.0 (C, rot A, rot B), 9.0 (C or C, rot B), 9.8 (C or C, rot A),. (C ), {.,.9,.08, 8.09, 8.9, 9. (C, C, x C(Ph), x C(Ph), C(Ph), C quat (Ph), rot A, rot B)},. (C (Ts), C (Ts) or C (Ts), C (Ts), rot A, rot B), 9.89 (C (Ts), C (Ts) or C (Ts), C (Ts), rot A, rot B), {.,.9,. (C a, C a, C quat (Ts), rot A, rot B)},. (C quat (Ts), rot A, rot B),.00 (C=, rot A, rot B); IR (KBr, cm - ):, 8 (ν C= ), 8,, (ν S ); MS (ESI): m/z = 8 (Ts-Ind-C + ); Mp.:. C.

13 This journal is The wner Societies 00 Reaction time: h, yield: %. -MR (00 Mz, CD, ppm):.8 (, d, J=. z, x C (ipr)),. (, s, C (Ts)),.9 (, s, (Ind)C ),.9-.9 (, m, C(iPr)),.8 (, d, J = 8. z, C (Ts), C (Ts)),. (, dxdxd, J = J =. z, J =. z, a C C or C ),. (, dxd, J = J =. z, C or C ),. (, s, C ),. (, d, J = 8.0 z, C or C ),.9 (, d, J = 8. z, C (Ts), C (Ts)),.98 (, d, J = 8.0 z, C or C ); C-MR (. Mz, CD, ppm): 0. (x S C (ipr)),.0 (C (Ts)), 8. ((Ind)C ), 0.9 (C(iPr)), 9. (C ),.9 and 9. (C and C ), 9.8 (C ),.8 (C or C ),.08 (C ),.9 (C or C ),. (C, C (Ts), C (Ts)), 9. (C a or C a ), b 9.8 (C, C (Ts), C (Ts)),.9 (C (Ts)),. (C a or C a ),.9 (C (Ts)), 0. (C=); IR (KBr, cm - ):, (ν C= ),, 9 (ν S= ); MS (ESI): m/z = 9// ([M +] + +); Mp.: 8. C. Procedure for the preparation of a A mixture of 0. g (0. mmol, equiv.) a and. mg (0.mmol, 0.8 equiv.) TMEDA was dissolved in refluxing C and was flushed with argon for minutes.. mg (0. mmol, 0. equiv.) Cu(I) was added to the reaction mixture. The reaction mixture was refluxed for h under argon atmosphere and finally quenched with water and stirred for 0 minutes. The organic phase was washed three times with water until the blue colour of the wash water disappeared. After drying over MgS, filtration and evaporation of the solvent the spiro compound was obtained. Crystallisation in chloroform/diethylether afforded the compound in % yield. -MR (00 Mz, CD, ppm): δ =.9 (, s, C ),.8 (, d, J AB = 0.9 z, (Ind)C ),.8 (, d, J AB = 0.9 z, (Ind)C ),.8 (, d, J AB =. z, C (Ph)),.0 (, d, J AB =. z, C (Ph)),. (, d, J =. z, C or C ), a S.9 (, dxd, J = J =. z, C or C ),.99 (, s, C ), a.-. (8, m, C or C, x C(Ph), x C(Ts)),.9 (, d, J = 8.0 z, C or C ),.88 (, d, J = 8.0 z, x C(Ts)); a C-MR (. Mz, CD, ppm): δ =. (C ), 8.0 (C (Ph)), 0.8 ((Ind)C ),. (C ), 80.9 (C ), 8. (C ),. (C or C ),. (C or C ),.8 (C or C ),.88 (C, x C(Ts)), 8.80 (C(Ph)), 8.90 (C, x C(Ph)), 9. (C, x C(Ph)), 9.8 (C a or C a or C quat (Ts)), 0.0 (C or C ),. (C, x C(Ts)),. (C quat (Ph)),. (C a or C a or C quat (Ts)), 9. (C a or C a or C quat (Ts)),.8 (C quat (Ts)),.8 (C=); IR (KBr, cm - ):, (ν C= ), 98,, (ν S ); MS (ESI): ): m/z = /9/ (M+ + ); Mp./decomposition temperature: 0. C.

14 This journal is The wner Societies 00 Crystallisation in methanol; yield: %. -MR (00 Mz, CD, ppm):. (, d, J =.9 z, C (ipr)), (, d, J =.9 z, C (ipr)),.9 (, s, C (Ts)),.0 (, d, J AB = 0. z, (Ind)C ),.88 (, d, J AB = 0. z, (Ind)C ),,9 (, sept, J =.9 z, C(iPr)),.0 (, s, C ),.0-. (, a m, C or C and C or C ),.0 (, d, J = 8.0 z, C (Ts), C (Ts)),.8 (, dxdxd, J = J =.9 z, J =.9 z, C or C ),. (, d, J = 8, z, C or C ),.90 (, d, J = 8. z, C (Ts), C (Ts)); S C-MR (, Mz, CD, ppm): 9. (C (ipr)), 9.0 (C (ipr)),. (C (Ts)),.0 (C(iPr)),. ((Ind)C ),. (C ), 8. (C ), 8. b (C ),.9 (C or C ),. and.8 (C or C and C or C ),.8 (C, C (Ts), C (Ts)), 9. (C a or C a ), 9.99 (C, C (Ts), C (Ts)),.0 (C or C ),.8, 9. and.0 (C quat (Ts), C a and C a ),.0 (C=); IR (KBr, cm - ): (ν C= ),, 9 (ν S= ); MS (ESI): m/z = 9// ([M +] + +); Mp./decomposition temperature:. C. GEERAL PRCEDURE FR TE SYTESIS F TE EMI-AMIAL 0. g of was dissolved in C together with 0. g silica. The mixture was stirred for h at room temperature. The silica was filtrated over celite and the solvent was concentrated in vacuo. The compound was obtained in 80 % yield. -MR (00 Mz, CD, ppm): δ =. (, s, C ),. a S a a (, d, J AB = 0. z, (Ind)C ),.0 (, d, J =.0 z, C, D exchangeable),.99 (, d, J AB = 0. z, (Ind)C ),. (, d, J AB =. z, C (Ph)),. (, d, J AB =. z, C (Ph)),.0 (, d, J =.0 z, C ),.8 (, dxd, J =. z, J = 0.8 z, C or C ),.89 (, dxdxd, J = J =. z, J = 0.8 z, C or C ),.-.0 (8, m, C or C, x C(Ph), x C(Ts)),.9 (, d, J = 8.0 z, C or C ),. (, d, J = 8. z, x C(Ts)); C-MR (. Mz, CD, ppm): δ =. (C ), 8. (C (Ph)), 9.9 ((Ind)C ),.8 (C ), 8.0 (C ), 8. (C ),.09 (C or C ),.8 (C or C ),. (C or C ),. (C, x C(Ph) or x C(Ts)), 8. (C(Ph)), 8.8 (C, x C(Ph) or x C(Ts)), 9. (C, x C(Ph) or x C(Ts)), 9.8 (C quat (Ts)), 0.0 (C, x C(Ph) or x C(Ts)), 0.8 (C or C ), {.,., 9. (C a, C a, C quat(ph))},.0 (C quat (Ts)),. (C=); IR (KBr, cm - ): (ν ), (ν C= ), 99, 8,, (ν S ); MS (ESI): ): m/z = /9/ (M+ + ); Mp./decomposition temperature: 0. C. yield: %. -MR (00 Mz, CD, ppm):. (, d, J =. z, C (ipr)),. (, d, J =. z, C (ipr)),. (, s, C (Ts)),. (, d, J AB = 0. z, (Ind)C ),. (, d, J =.0 z, ),.0 (, d, J AB = 0. z, (Ind)C ),. (, sept, a J =.9 z, C(iPr)),.0 (, d, J =.0 z, C ),.0 (, d, J = 8.0 z, C or C ),.0 (, dxdxd, J = J = 8.0 z, J =. z, C or C ),. (, d, J = 8. z, C (Ts), C (Ts)),. (, dxd, J = J =. z, C or C ),. (, d, J = 8.0 z, C or C ),.8 (, d, J = 8. z, C (Ts), C (Ts)); C-MR (, S Mz, CD, ppm): 9. (C (ipr)), 9. (C (ipr)),. (C (Ts)),. (C, (Ind)C, C(iPr)), 0.9 (C ), 8.8 (C ), 8.9 (C ),.0 (C or b C ),.9 (C or C ),. (C or C ),.8 (C, C (Ts), C (Ts)), 9. (C a ), 9.99 (C, C (Ts), C (Ts)), 0.80 (C or C ),.8 (C (Ts)), 0. (C a ),.0 (C (Ts)),. (C=); IR (KBr, cm - ): 0 (ν ), 9 (ν C= ), 8, 9 (ν S= ); MS (ESI): m/z = 9// (M + +); Mp.: 9. C.