Highly Diastereo- and Enantioselective Organocatalytic Domino Michael/Aldol Reaction of Acyclic 3- Halogeno- 1,2- Diones to α,β- Unsaturated Aldehydes

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1 Supporting Information for Highly Diastereo- and Enantioselective rganocatalytic Domino Michael/Aldol Reaction of Acyclic 3- Halogeno- 1,2- Diones to α,β- Unsaturated Aldehydes Alice Lefranc 1, Laure Guénée 2, Alexandre Alexakis 1, * 1 Department of rganic Chemistry, University of Geneva, 30 quai Ernest- Ansermet, 1211 Geneva 4, Switzerland. 2 Laboratory of crystallography, University of Geneva, 24 quai Ernest- Ansermet, 1211 Geneva 4, Switzerland. Alexandre.Alexakis@unige.ch Table of contents General remarks 2 General procedure for the synthesis of 3-chloro-1,2-diones 2 General procedure for the organocatalytic domino Michael/aldol reaction of 3-chloro-1,2-diones to α,β-unsaturated aldehydes 7 Procedure for the synthesis of 3-fluoro-1,3-diphenylpropane-1,2- dione 5 16 Procedure for the organocatalytic domino Michael/aldol reaction of 3- fluoro-1,3-diphenylpropane-1,2-dione 6 to cinnamaldehyde 16 SFC chromatograms 18 NMR spectra 36 Crystallographic data 98 1

2 I. General remarks: 1 H (400 MHz or 300 MHz), 13 C (100 MHz or 75 MHz), 19 F (376 MHz) spectra were recorded on either a Bruker 300 MHz, or 400 MHz spectrometer at room temperature and are reported as chemical shift (δ) in ppm relative to solvent peak. Spin multiplicity are reported as singlet (s), doublet (d), triplet (t), doublet of doublet (dd), triplet of doublet (td) and multiplet (m). Coupling constant J is given in Hertz (Hz). ptical rotation were measured at 22 C in a 10 cm cell in the stated solvent; [α] D values are given in 10-1 deg.cm 2 g - 1 (concentration c given as g/100 ml). Melting points (mp) were measured in open capillary tubes and are uncorrected. Electrospray mass spectra were obtained by the Sciences Mass Spectrometry (SMS) platform at the Faculty of Sciences (University of Geneva) on a QStar pulsar instrument from AB/MDS Sciex, ESI. Enantiomeric excesses were determined by chiral super fluid chromatography (SFC) with an appropriate program using a gradient of isopropanol, Temperature = 30 C, initial pourcentage of isopropanol (%) - isopropanol gradient (%/min)- final pourcentage of isopropanol (%); retention time (RT) are given in minute. X-ray data were measured using Cu radiation on a SuperNova Dual source equipped with an Atlas detector.flash chromatography was performed using silica gel µm, 60 Å. Methylene chlroride was dried on aluminia columns. The other commercial solvents were used directly without any drying or purifications before use. TMS (98%, Acros) distilled on calcium hydride. bmimpf 6 (Sigma Aldrich), DMP (Alpha Aesar), cinnamaldehyde 2a (Sigma Aldrich), trans- 4- methoxycinnamaldehyde 2c (Acros), 3- (2- furyl)acrolein 2i (Acros) and (S)- α,α- Bis[3,5- bis(trifluoromethyl)phenyl]- 2- pyrrolidinemethanol trimethylsilyl ether (Sigma Aldrich) were purchased and used as received. The following substrates 7a- k were prepared according to literature procedures: aldol condensation between the corresponding acetophenone and aldehyde 1 ; then epoxydation of the obtained α,β- unsaturated ketone 2. The substrates 2b, 2d- h and 9 have been prepared according to literature procedure 3,4. II. General procedure for the synthesis of 3-chloro-1,2-diones: 1)TMS, bmimpf 6, rt, 24h DMP R 1 R 2 2) sat. NH 4 solution R 1 R 2 H CH 2 2, rt, 4h R 1 R 2 7a-k 8a-k 1a-k General procedure: A suspension of epoxy ketone 7a- k (1.0 equiv.), freshly distilled Me 3 Si (1.5 equiv.), and bmimpf 6 (1 M) were stirred at ambient temperature under an inert atmosphere for 24 h. After completion of the reaction, as indicated by TLC, the resultant yellow reaction mixture was diluted with saturated aqueous NH 4, and extracted with diethyl ether. The combined organic layers were dried over anhydrous Na 2 S 4, filtered and concentrated in vacuo. Product 8a- k, 3- chloro- 2- hydroxy- ketone, was directly involved in the next step without purification 5. To a well- stirred mixture of 3- chloro- 2- hydroxy- ketone 8a- k (1.0 equiv.) in anhydrous CH 2 2 (0.15 M) was added Dess- Martin periodinane (1.2 equiv.) portionwise as a solid. The resultant yellow solution was stirred at ambient temperature under an inert atmosphere for 4 h. The mixture was poured into 10% (w/w) aqueous Na 2 S 2 3 and extracted twice with CH 2 2. The combined organic layers were washed with water, then brine, dried over anhydrous Na 2 S 4, filtered and concentrated under 2

3 reduced pressure. The crude product was purified by flash chromatography on silica gel (c- hexane/etac), affording the corresponding diketone 1a- k. Product 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a: C 15 H 11 2 MW: g.mo l-1 General procedure using 1,3- diphenyl- 2,3- epoxy- 1- propanone (449 mg, 2.0 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2mL). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13mL). Purification by flash chromatography (c- hexane/etac 99:1) gave 1a as a yellow solid. Yield : 64% (328 mg, 1.27 mmol). R f (silica gel, c- Hex/EtAc 4:1) H NMR (CD 3, 400 MHz) δ 7.90 (d, J = 7.2 Hz, 2H, C ar - H), 7.62 (t, J = 7.9 Hz, 1H, C ar - H), (m, 4H, C ar - H), (m, 3H, C ar - H), 6.33 (s, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 61.8 (CH). I.R. (thin film) ν 1731, 1665, 1592, 1447, 1269, 1192, 688, 668 cm - 1. Mp C. HRMS (ESI) for C 15 H 11 2 [M- H] - : calcd , found Product 3- chloro- 1- (o- chloro)phenyl- 3- phenylpropane- 1,2- dione 1b: C 15 H MW: g.mol -1 General procedure using 1- (o- chloro)phenyl- 3- phenyl- 2,3- epoxy- 1- propanone (515 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1b as a yellow oil. Yield : 54% (314 mg, 1.07 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 300 MHz) δ 7.59 (dd, J = 1.5, 7.7 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 5H, C ar - H), 6.29 (s, 1H, CH). 13 C NMR (CD 3, 75 MHz) δ (ketone Cq), (ketone Cq), (C ar - H), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 61.3 (CH). I.R. (thin film) ν 1729, 1684, 1588, 1437, 1295, 1225, 1053, 907, 752, 740, 691, 634 cm - 1. HRMS (ESI) for C 15 H [M- H] - : calcd , found Product 3- chloro- 1- (p- bromo)phenyl- 3- phenylpropane- 1,2- dione 1c : Br C 15 H 10 Br 2 MW: g.mol -1 General procedure using 1- (p- bromo)phenyl- 3- phenyl- 2,3- epoxy- 1- propanone (606 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1c as a yellow solid. Yield : 61% (410 mg, 1.21 mmol). R f (silica gel, c- Hex/EtAc 9:1)

4 1 H NMR (CD 3, 400 MHz) δ 7.77 (d, J = 8.6 Hz, 2H, C ar - H), 7.60 (d, J = 8.6 Hz, 2H, C ar - H), 7.45 (dd, J = 1.6, 7.9 Hz, 2H, C ar - H), (m, 3H, C ar - H), 6.32 (s 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (Cq), (C ar - H), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), 61.6 (CH). I.R. (thin film) ν 1726, 1676, 1582, 1486, 1285, 1201, 1102, 1069, 1009, 898, 851, 730, 710, 650 cm - 1. Mp C. HRMS (ESI) for C 15 H 10 Br 2 [M- H] - : calcd , found Product 3- chloro- 1- (p- methoxy)phenyl- 3- phenylpropane- 1,2- dione 1d: Me C 16 H 13 3 MW: g.mol -1 General procedure using 1- (p- methoxy)phenyl- 3- phenyl- 2,3- epoxy- 1- propanone (508 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 90:10) gave 1d as a yellow oil. Yield : 58% (332 mg, 1.15 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 300 MHz) δ 7.90 (d, J = 8.9 Hz, 2H, C ar - H), 7.46 (d, J = 6.3 Hz, 2H, C ar - H), (m, 3H, C ar - H), 6.91 (d, J = 8.9 Hz, 2H, C ar - H), 6.35 (s, 1H, CH), 3.84 (s, 3H, CH 3 ). 13 C NMR (CD 3, 75 MHz) δ (ketone Cq), (ketone Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (Cq), (C ar - H), 61.9 (CH), 55.7 (CH 3 ). I.R. (thin film) ν 1728, 1657, 1593, 1572, 1511, 1260, 1172, 1091, 1023, 905, 829, 714, 694 cm - 1. HRMS (ESI) for C 16 H 13 3 [M+H] + : calcd , found Product 3- chloro- 1- (m- methyl)phenyl- 3- phenylpropane- 1,2- dione 1e : General procedure using 1- (m- methyl)phenyl- 3- phenyl- 2,3- epoxy- 1- propanone (331 mg, 1.4 mmol), Me 3 Si (266 μl, 2.1mmol) and bmimpf 6 (1.4 ml). Then DMP (686 mg, 1.7 mmol) and CH 2 2 (9 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1e as a yellow oil. Yield : 61% (234 mg, 0.86 mmol). R f (silica gel, c- Hex/EtAc 9:1) C 16 H 13 2 MW: g.mol -1 1 H NMR (CD 3, 300 MHz) δ (m, 2H, C ar - H), (m, 7H, C ar - H), 6.32 (s, 1H, CH), 2.38 (s, 3H, CH 3 ). 13 C NMR (CD 3, 75 MHz) δ (ketone Cq), (ketone Cq), (Cq), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 61.8 (CH), 21.4 (CH 3 ). I.R. (thin film) ν 1731, 1666, 1601, 1581, 1454, 1285, 1188, 1096, 948, 860, 702, 638 cm - 1. HRMS (ESI) for C 16 H 13 2 [M- H] - : calcd , found Product 3- chloro- 1,3- bis(p- chloro)phenylpropane- 1,2- dione 1f : General procedure using 1- (p- chloro)phenyl- 3- (p- chloro)phenyl- 2,3- epoxy- 1- propanone (586 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and C 15 H MW: g.mol -1 4

5 CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1f as a yellow solid. Yield : 48% (311 mg, 0.95 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 400 MHz) δ 7.89 (d, J = 8.3Hz, 2H, C ar - H), 7.45 (d, J = 8.3 Hz, 2H, C ar - H), (m, 4H, C ar - H), 6.29 (s, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (Cq), (Cq), (C ar - H), (Cq), (C ar - H), (2C ar - H and Cq), 60.3 (CH). I.R. (thin film) ν 1719, 1676, 1586, 1490, 1402, 1285, 1262, 1193, 1089, 1012, 910, 853, 805, 750, 724, 643 cm - 1. Mp C. HRMS (ESI) for C 15 H [M- H] - : calcd , found Product 3- chloro- 3- (m- methoxy)phenyl- 1- phenylpropane- 1,2- dione 1g: Me C 16 H 13 3 MW: g.mol -1 General procedure using 1- phenyl- 3- (m- methoxy)phenyl- 2,3- epoxy- 1- propanone (440 mg, 1.7 mmol), Me 3 Si (332 μl, 2.6 mmol) and bmimpf 6 (1.7 ml). Then DMP (807 mg, 2.0 mmol) and CH 2 2 (12 ml). Purification by flash chromatography (c- hexane/etac 95:5) gave 1g as a yellow oil. Yield : 49% (243 mg, 0.84 mmol). R f (silica gel, c- Hex/EtAc 9,5:5) H NMR (CD 3, 300 MHz) δ 7.91 (d, J = 7.5 Hz, 2H, C ar - H), 7.62 (t, J = 7.4 Hz, 1H, C ar - H), 7.46 (t, J = 7.7 Hz, 2H, C ar - H), 7.29 (t, J = 7.9 Hz, 1H, C ar - H), (m, 2H, C ar - H), 6.88 (d, J = 8.3 Hz, 1H, C ar - H), 6.31 (s, 1H, CH), 3.79 (s, 3H, CH 3 ). 13 C NMR (CD 3, 75 MHz) δ 191,3 (ketone Cq), (ketone Cq), (Cq), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 61.8 (CH), 55.5 (CH 3 ). I.R. (thin film) ν 1728, 1670, 1597, 1490, 1451, 1262, 1041, 760, 732, 685, 640 cm - 1. HRMS (ESI) for C 16 H 13 2 [M+H] + : calcd , found Product 3- chloro- 3- (p- methyl)phenyl- 1- phenylpropane- 1,2- dione 1h : C 16 H 13 2 MW: g.mol -1 General procedure using 1- phenyl- 3- (p- methyl)phenyl- 2,3- epoxy- 1- propanone (476 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1h as a yellow solid. Yield : 69% (374 mg, 1.38 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 400 MHz) δ 7.90 (d, J = 7.1 Hz, 2H, C ar - H), 7.62 (t, J = 7.4 Hz, 1H, C ar - H), 7.46 (t, J = 7.7 Hz, 2H, C ar - H), 7.35 (t, J = 8.1 Hz, 2H, C ar - H), 7.19 (d, J = 8.0 Hz, 2H, C ar - H), 6.30 (s, 1H, CH), 2.33 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (Cq), (Cq), (Cq), 130.3(C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 61.8 (CH), 21.4 (CH 3 ). I.R. (thin film) ν 1725, 1675, 1585, 1290, 1104, 1075, 847, 814, 732, 702, 651 cm - 1. Mp C. 5

6 HRMS (ESI) for C 16 H 13 2 [M- H] - : calcd , found Product 3- chloro- 3- (p- nitro)phenyl- 1- phenylpropane- 1,2- dione 1i: C 15 H 10 N 4 MW: g.mol -1 N 2 General procedure using 1- phenyl- 3- (p- nitro)phenyl- 2,3- epoxy- 1- propanone (538 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 90:10) gave 1i as a yellow solid. Yield : 13% (78 mg, 0.26 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 400 MHz) δ 8.28 (d, J = 8.8 Hz, 2H, C ar - H), 7.98 (dd, J = 1.3, 8.3 Hz, 2H, C ar - H), (m, 3H, C ar - H), 7.52 (t, J = 7.8 Hz, 2H, C ar - H), 6.37 (s, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ190,3 (ketone Cq), (ketone Cq), (Cq), (Cq), (C ar - H), (Cq), 130.4(C ar - H), (C ar - H), (C ar - H), (C ar - H), 59.4 (CH). I.R. (thin film) ν 1725, 1668, 1595, 1519, 1345, 1313, 1268, 1098, 833, 771, 728, 683, 638, 612 cm - 1. Mp C. HRMS (ESI) for C 15 H 10 N 4 [M- H] - : calcd , found Product 3- chloro- 3- (o- bromo)phenyl- 1- phenylpropane- 1,2- dione 1j : Br C 15 H 10 Br 2 MW: g.mol -1 General procedure using 1- phenyl- 3- (o- bromo)phenyl- 2,3- epoxy- 1- propanone (604 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1j as a yellow oil. Yield : 50% (338 mg, 1.0 mmol). R f (silica gel, c- Hex/EtAc 9:1) H NMR (CD 3, 400 MHz) δ 7.97 (d, J = 7.4Hz, 2H, C ar - H), (m, 3H, C ar - H), 7.43 (t, J = 7.5 Hz, 2H, C ar - H), 7.33 (t, J = 7.5 Hz, 1H, C ar - H), 7.17 (t, J = 7.6 Hz, 1H, C ar - H), 6.78 (s, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (C ar - H), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (Cq), 60.2 (CH). I.R. (thin film) ν 1731, 1672, 1596, 1448, 1261, 1235, 1095, 1027, 906, 857, 735, 715, 683, 637 cm - 1. HRMS (ESI) for C 15 H 10 Br 2 [M+H] + : calcd , found Product 3- chloro- 3- (o- methyl)phenyl- 1- phenylpropane- 1,2- dione 1k : C 16 H 13 2 MW: g.mol -1 General procedure using 1- phenyl- 3- (o- methyl)phenyl- 2,3- epoxy- 1- propanone (477 mg, 2 mmol), Me 3 Si (383 μl, 3 mmol) and bmimpf 6 (2 ml). Then DMP (968 mg, 2.4 mmol) and CH 2 2 (13 ml). Purification by flash chromatography (c- hexane/etac 99:1) gave 1k as a yellow oil. Yield : 62% (335 mg, 1.23 mmol). R f (silica gel, c- Hex/EtAc 9:1)

7 1 H NMR (CD 3, 400 MHz) δ 7.96 (d, J = 7.8 Hz, 2H, C ar - H), 7.61 (t, J = 7.4 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 3H, C ar - H), 6.64 (s, 1H, CH), 2.48 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (ketone Cq), (Cq), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 59.3 (CH), 19.4 (CH 3 ). I.R. (thin film) ν 1730, 1666, 1594, 1451, 1312, 1279, 1233, 1098, 914, 861, 771, 738, 709, 681, 630 cm - 1. Mp C. HRMS (ESI) for C 16 H 13 2 [M- H] - : calcd , found III. General procedure for the organocatalytic domino Michael/aldol reaction of 3-chloro-1,2-diones to α,β-unsaturated aldehydes: R 1 R 2 R 3 N H Ar Ar TMS Ar: 3,5-(CF 3 ) 2 Ph 20 mol% Toluene, rt, 30min R 1 H R 2 1a-k 2a-h R 3 3a-r To a solution of the corresponding derivative cinnamaldehyde 2a- i (2.0 equiv.) in Toluene (1 M) were added successively the diarylprolinol silylether catalyst II (20 mol%) and the corresponding diketone 1a- k (1.0 equiv.). The mixture was stirred at room temperature for 30 minutes. Then mixture was quenched with 1 ml of 1M H solution and extracted three times with 5 ml of CH 2 2. The combined organic layers were dried over anhydrous Na 2 S 4, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (c- hexane/etac), affording the corresponding cyclopentanone 3a- q. Product 3a : H C 24 H 19 3 MW: g.mol -1 Hex/EtAc 9:1) : General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (26 mg, 0.1 mmol), cinnamaldehyde 2a (26.4 mg, 0.2 mmol) and the diarylprolinol silylether catalyst II (12 mg, 0.02 mmol) in Toluene (0.2 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96 :4) gave 3a as a pale yellow oil. Yield : 97% (38.1 mg, 97.4 µmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- 7

8 The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.70 min, t 2 = min. [α] 22 D = (c= 0.39 in CH 3, 88% ee). 1 H NMR (CD 3, 400 MHz) δ 9.81 (d, J = 1.8Hz, 1H, aldehyde), 7.62 (d, J = 7.2 Hz, 2H, C ar - H), 7.50 (t, J = 7.3 Hz, 2H, C ar - H), 7.47 (d, J = 7.1 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 2H, C ar - H), (m, 1H, C ar - H), 7.21 (t, J = 7.4 Hz, 2H, C ar - H), 6.86 (d, J = 7.3 Hz, 2H, C ar - H), 4.54 (d, J = 12.4 Hz, 1H, CH), 4.00 (d, J = 12.4 Hz, 1H, CH), 3.38 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.9 (Cq), 77.8 (Cq), 60.1 (CH), 54.1 (CH). I.R. (thin film) ν 3379, 1762, 1721, 1497, 1448, 1373, 1279, 1136, 907, 732, 697, 607 cm - 1. HRMS (ESI) for C 24 H 19 3 [(M- H)- H] - : calcd , found Product 3b : H General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- m- methoxycinnamaldehyde 2b (64.9 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3b as a pale yellow oil. Yield : 83% (70 mg, 0.17 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.44 in CH 3, 90% ee). 1 H NMR (CD 3, 300 MHz) δ 9.82 (s, 1H, aldehyde), 7.62 (d, J = 7.0 Hz, 2H, C ar - H), 7.50 (t, J = 7.1 Hz, 2H, C ar - H), 7.45 (d, J = 7.9 Hz, 1H, C ar - H), (m, 5H, C ar - H), 7.13 (t, J = 7.9 Hz, 1H, C ar - H), 6.81 (d, J = 8.1 Hz, 1H, C ar - H), 6.48 (d, J = 7.6 Hz, 1H, C ar - H), 6.32 (s, 1H, C ar - H), 4.51 (d, J = 12.4 Hz, 1H, CH), 3.97 (d, J = 12.4 Hz, 1H, CH), 3.61 (s, 3H, CH 3 ), 3.34 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.8 (Cq), 77.7 (Cq), 60.1 (CH), 55.1 (CH 3 ), 53.9 (CH). I.R. (thin film) ν 3414, 1761, 1721, 1601, 1493, 1448, 1279, 1140, 1042, 737, 695 cm - 1. Mp C. HRMS (ESI) for C 25 H 21 4 [(M- H)- H] - : calcd , found Product 3c : H C 25 H 21 4 MW: g.mol -1 C 25 H 21 4 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- p- methoxycinnamaldehyde 2c (64.9 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3c as a pale yellow oil. Yield : 77% (69.2 mg, 0.15 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. 8

9 [α] 22 D = (c= 0.38 in CH 3, 86% ee). 1 H NMR (CD 3, 400 MHz) δ 9.79 (d, J = 2.0 Hz, 1H, aldehyde), 7.60 (d, J = 7.0 Hz, 2H, C ar - H), 7.49 (t, J = 7.0 Hz, 2H, C ar - H), 7.44 (d, J = 7.1 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 2H, C ar - H), 6.80 (d, J = 8.9 Hz, 2H, C ar - H), 6.75 (d, J = 8.9 Hz, 2H, C ar - H), 4.48 (d, J = 12.5 Hz, 1H, CH), 3.92 (d, J = 12.5 Hz, 1H, CH), 3.76 (s, 3H, CH 3 ), 3.44 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), 128.8(C ar - H), (C ar - H), (C ar - H), (C ar - H), (Cq), (C ar - H), 81.9 (Cq), 78.0 (Cq), 60.3 (CH), 55.3 (CH 3 ), 53.5 (CH). I.R.(thin film)ν 3405, 1761, 1722, 1612, 1514, 1447, 1250, 1180, 1065, 1031, 907, 829, 728, 696 cm - 1. HRMS (ESI) for C 25 H 21 4 [(M- H)- H] - : calcd , found Product 3d : H C 25 H 21 3 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- p- methylcinnamaldehyde 2d (58.4 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3d as a pale yellow oil. Yield : 90% (73 mg, 0.18 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 20% Isopropanol- 1%/min- 35% Isopropanol in C 2, 30 C, t 1 = 5.39 min, t 2 = 6.71 min. [α] 22 D = (c= 0.30 in CH 3, 86% ee). 1 H NMR (CD 3, 400 MHz) δ 9.78 (d, J = 2.0 Hz, 1H, aldehyde), 7.60 (d, J = 6.9 Hz, 2H, C ar - H), 7.48 (t, J = 7.3 Hz, 2H, C ar - H), 7.43 (d, J = 7.3 Hz, 1H, C ar - H), (m, 5H, C ar - H), 7.03 (d, J = 7.9 Hz, 2H, C ar - H), 6.76 (d, J = 7.9 Hz, 2H, C ar - H), 4.51 (d, J = 12.5 Hz, 1H, CH), 3.96 (d, J = 12.4 Hz, 1H, CH), 3.60 (s, 1H, H), 2.30 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), 129.1(2C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.9 (Cq), 77.8 (Cq), 60.2 (CH), 53.7 (CH), 21.2 (CH 3 ). I.R. (thin film) ν 3308, 1754, 1719, 1446, 1279, 1141, 1065, 906, 818, 731, 694, 594 cm - 1. Mp C. HRMS (ESI) for C 25 H 21 3 [(M- H)- H] - : calcd , found Product 3e : H C 25 H 21 4 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- o- methoxycinnamaldehyde 2e (60 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3e as a pale yellow oil. Yield : 83% (76.6 mg, 0.17 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.60 in CH 3, 82% ee). 1 H NMR (CD 3, 400 MHz) δ 9.65 (d, J = 2.0 Hz, 1H, aldehyde), 7.53 (d, J = 7.2 Hz, 2H, C ar - H), 7.40 (t, J 9

10 = 7.3 Hz, 2H, C ar - H), (m, 1H, C ar - H), (m, 7H, C ar - H), 6.87 (t, J = 7.5 Hz, 1H, C ar - H), 6.60 (d, J = 8.2 Hz, 1H, C ar - H), 5.06 (d, J = 12.8 Hz, 1H, CH), 3.84 (d, J = 13.6 Hz, 1H, CH), 3.53 (s, 1H, H), 3.02 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (2C ar - H), (C ar - H), (2C ar - H), (Cq), (C ar - H), (C ar - H), 81.9 (Cq), 78.1 (Cq), 60.4 (CH), 54.7 (CH 3 ), 46.5 (CH). I.R. (thin film) ν 3511, 1755, 1723, 1494, 1276, 1250, 1141, 1095, 1031, 751, 696, 608 cm - 1. Mp C. HRMS (ESI) for C 25 H 21 4 [(M- H)- H] - : calcd , found Product 3f : min. H F C 24 H 18 F 3 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- p- fluorocinnamaldehyde 2f (60 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3f as a pale yellow oil. Yield : 94% (76.6 mg, 0.19 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 8.46 min, t 2 = 9.83 [α] 22 D = (c= 0.67 in CH 3, 90% ee). 1 H NMR (CD 3, 400 MHz) δ 9.77 (s, 1H, aldehyde), 7.59 (d, J = 7.0 Hz, 2H, C ar - H), 7.48 (t, J = 6.8 Hz, 2H, C ar - H), 7.44 (d, J = 7.0 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 2H, C ar - H), (m, 2H, C ar - H), 6.90 (t, J = 8.7 Hz, 2H, C ar - H), 4.49 (d, J = 12.4 Hz, 1H, CH), 3.91(d, J = 12.4 Hz, 1H, CH), 3.55 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (d, J C- F = Hz, Cq), (Cq), (Cq), (d, J C- F = 8.1 Hz, C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (d, J C- F = 3.3 Hz, Cq), (C ar - H), (C ar - H), (d, J C- F = 21.4 Hz, C ar - H), 81.6 (Cq), 77.7 (Cq), 60.5 (CH), 53.3 (CH). I.R. (thin film) ν 3352, 1760, 1713, 1604, 1511, 1448, 1368, 1280, 1227, 1139, 1068, 831, 803, 742, 699, 611 cm - 1. Mp C. HRMS (ESI) for C 24 H 18 F 3 [(M- H)- H] - : calcd , found Product 3g : H Br C 24 H 18 Br 3 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- m- bromocinnamaldehyde 2g (84.4 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3g as a pale yellow oil. Yield : 92% (86.6 mg, 0.18 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) :

11 The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.57 in CH 3, 88% ee). 1 H NMR (CD 3, 400 MHz) δ 9.80 (d, J = 1.7 Hz, 1H, aldehyde), 7.62 (d, J = 7.0 Hz, 2H, C ar - H), 7.50 (t, J = 8.0 Hz, 2H, C ar - H), 7.46 (d, J = 7.0 Hz, 1H, C ar - H), (m, 4H, C ar - H), (m, 2H, C ar - H), 7.06 (t, J = 7.9 Hz, 1H, C ar - H), 7.00 (s, 1H, C ar - H), 6.72 (d, J = 7.8 Hz, 1H, C ar - H), 4.47 (d, J = 12.3 Hz, 1H, CH), 3.94 (d, J = 12.3 Hz, 1H, CH), 3.24 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (Cq), 81.6 (Cq), 77.4 (Cq), 60.2 (CH), 53.5 (CH). I.R. (thin film) ν 3432, 1762, 1723, 1279, 1140, 1070, 906, 729, 693 cm - 1. HRMS (ESI) for C 24 H 18 Br 3 [(M- H)- H] - : calcd , found Product 3h : H General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), trans- o- bromocinnamaldehyde 2h (84.4 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3h as a yellow solid. Yield : 85% (80.3 mg, 0.17 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AD- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.51 in CH 3, 83% ee). 1 H NMR (CD 3, 400 MHz) δ 9.71 (d, J = 1.7 Hz, 1H, aldehyde), 7.61 (d, J = 7.2 Hz, 2H, C ar - H), (m, 5H, C ar - H), (m, 4H, C ar - H), (m, 2H, C ar - H), 7.14 (dt, J = 1.6, 7.2 Hz, 1H, C ar - H), 5.09 (d, J = 12.4 Hz, 1H, CH), 3.84 (dd, J = 1.7, 12.4 Hz, 1H, CH), 3.49 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (C ar - H), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (Cq), (C ar - H), (C ar - H), 81.6 (Cq), 77.2 (Cq), 62.0 (CH), 51.8 (CH). I.R. (thin film) ν 3446, 1761, 1720, 1446, 1280, 1140, 1096, 1025, 906, 797, 727, 695, 605 cm - 1. Mp C. HRMS (ESI) for C 24 H 18 Br 3 [(M- H)- H] - : calcd , found Product 3i : Br C 24 H 18 Br 3 MW: g.mol -1 H C 22 H 17 4 MW: g.mol -1 General procedure using 3- chloro- 1,3- diphenylpropane- 1,2- dione 1a (51.7 mg, 0.2 mmol), 3- (2- furyl)acrolein 2i (48.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 97:3) gave 3i as a pale yellow oil. Yield : 81% (61.6 mg, 0.16 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 10, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 8.59 min, t 2 = 9.03 min. [α] 22 D = (c= 0.55 in CH 3, 82% ee). 11

12 1 H NMR (CD 3, 400 MHz) δ 9.85 (d, J = 1.2 Hz, 1H, aldehyde), (m, 2H, C ar - H), (m, 2H, C ar - H), (m, 2H, C ar - H), (m, 4H, C ar - H), 7.32 (d, J = 1.0 Hz, 1H, C ar - H), 6.31 (dd, J = 1.5, 2.6 Hz, 1H, C ar - H), 6.00 (d, J = 2.6 Hz, 1H, C ar - H), 4.71 (d, J = 9.6 Hz, 1H, CH), 3.98 (d, J = 9.6 Hz, 1H, CH), 3.23 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (C ar - H), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.4 (Cq), 76.0 (Cq), 59.7 (CH), 47.5 (CH). I.R. (thin film) ν 3464, 1763, 1725, 1279, 1266, 1142, 1065, 1012, 946, 733, 695 cm - 1. HRMS (ESI) for C 22 H 17 4 [M+H] + : calcd , found Product 3j : H C 24 H MW: g.mol -1 General procedure using 3- chloro- 1- (o- chloro)phenyl- 3- phenylpropane- 1,2- dione 1b (58.6 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3j as a yellow solid. Yield : 80% (68 mg, 0.16 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.39 in CH 3, 94% ee). 1 H NMR (CD 3, 400 MHz) δ 9.70 (d, J = 1.9 Hz, 1H, aldehyde), (m, 1H, C ar - H), (m, 3H, C ar - H), (m, 5H, C ar - H), (m, 3H, C ar - H), 6.99 (d, J = 6.6 Hz, 2H, C ar - H), 4.67 (d, J = 12.4 Hz, 1H, CH), 4.50 (dd, J = 1.7, 12.4 Hz, 1H, CH), 4.07 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 128.5(C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.6 (Cq), 75.9 (Cq), 56.0 (CH), 54.5 (CH). I.R. (thin film) n 3459, 1774, 1720, 1497, 1441, 1356, 1280, 1183, 1139, 1033, 913, 753, 693, 611, 585 cm - 1. Mp C. HRMS (ESI) for C 24 H [(M- H)- H] - : calcd , found Product 3k : Br H C 24 H 18 Br 3 MW: g.mol -1 General procedure using 3- chloro- 1- (p- bromo)phenyl- 3- phenylpropane- 1,2- dione 1c (67.6 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3k as a yellow solid. Yield : 85% (79.5 mg, 0.17 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.64 in CH 3, 89% ee). 1 H NMR (CD 3, 400 MHz) δ 9.78 (d, J = 2.1 Hz, 1H, aldehyde), 7.65 (d, J = 8.7 Hz, 2H, C ar - H), 7.51 (d, J = 8.7 Hz, 2H, C ar - H), (m, 3H, C ar - H), (m, 3H, C ar - H), 7.26 (t, J = 7.5 Hz, 2H, C ar - H), 12

13 6.88 (d, J = 7.3 Hz, 2H, C ar - H), 4.54 (d, J = 12.5 Hz, 1H, CH), 3.96 (d, J = 12.4 Hz, 1H, CH), 3.47 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (C ar - H), (Cq), (C ar - H), 129.0(C ar - H), (C ar - H), (C ar - H), (C ar - H), 127.8(C ar - H), (C ar - H), (Cq), 81.6 (Cq), 77.8 (Cq), 59.8 (CH), 54.2 (CH). I.R. (thin film) ν 3449, 1756, 1725, 1489, 1448, 1279, 1138, 1073, 1009, 906, 794, 731, 697, 608 cm - 1. Mp C. HRMS (ESI) for C 24 H 18 Br 3 [(M- H)- H] - : calcd , found Product 3l : H C 25 H 21 4 MW: g.mol -1 General procedure using 3- chloro- 1- (p- methoxy)phenyl- 3- phenylpropane- 1,2- dione 1d (57.7 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3l as a yellow oil. Yield : 95% (79.9 mg, 0.19 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = min, t 2 = min. [α] 22 D = (c= 0.51 in CH 3, 90% ee). 1 H NMR (CD 3, 400 MHz) δ 9.80 (d, J = 2.0 Hz, 1H, aldehyde), 7.51 (d, J = 8.5 Hz, 2H, C ar - H), (m, 3H, C ar - H), (m, 2H, C ar - H), 7.27 (t, J = 7.3 Hz, 1H, C ar - H), 7.21 (d, J = 7.3 Hz, 2H, C ar - H), 7.00 (d, J = 8.8 Hz, 2H, C ar - H), 6.85 (d, J = 7.2 Hz, 2H, C ar - H), 4.52 (d, J = 12.4 Hz, 1H, CH), 3.97 (d, J = 12.4 Hz, 1H, CH), 3.85 (s, 3H, CH 3 ), 3.34 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.6 (Cq), 77.8 (Cq), 60.1 (CH), 55.5 (CH 3 ), 53.9 (CH). I.R. (thin film) ν 3447, 1757, 1722, 1610, 1513, 1447, 1250, 1181, 1142, 1064, 1030, 907, 832, 791, 732, 693, 597 cm - 1. HRMS (ESI) for C 25 H 21 4 [(M- H)- H] - : calcd , found Product 3m : H C 25 H 21 3 MW: g.mol -1 General procedure using 3- chloro- 1- (o- chloro)phenyl- 3- phenylpropane- 1,2- dione 1e (54.5 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3m as a yellow oil. Yield : 95% (76.8 mg, 0.19 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.18 min, t 2 = min. [α] 22 D = (c= 0.35 in CH 3, 88% ee). 1 H NMR (CD 3, 400 MHz) δ 9.80 (d, J = 1.7 Hz, 1H, aldehyde), (m, 8H, C ar - H), (m, 4H, C ar - H), 6.87 (d, J = 7.3 Hz, 2H, C ar - H), 4.53 (d, J = 12.4 Hz, 1H, CH), 4.00 (dd, J = 1.7, 12.4 Hz, 1H, 13

14 CH), 3.36 (s, 1H, H), 2.44 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), 129.4(C ar - H), (C ar - H), 128.8(C ar - H), (C ar - H), (C ar - H), (C ar - H), 127.8(C ar - H), (C ar - H), 123.0(C ar - H), 81.8 (Cq), 77.7 (Cq), 60.1 (CH), 54.0 (CH), 21.8 (CH 3 ). I.R. (thin film) ν 3392, 1762, 1722, 1497, 1448, 1365, 1279, 1138, 1083, 908, 783, 729, 695, 606 cm - 1. HRMS (ESI) for C 25 H 21 3 [(M- H)- H] - : calcd , found H Product 3n: General procedure using 3- chloro- 1,3- bis(p- chloro)phenylpropane- 1,2- dione 1f (65.5 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3n as a yellow oil. Yield : 75% (65 mg, 0.15 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.79 min, t 2 = min. [α] 22 D = (c= 0.40 in CH 3, 91% ee). 1 H NMR (CD 3, 400 MHz) δ 9.66 (d, J = 2.0 Hz, 1H, aldehyde), 7.43 (d, J = 8.8 Hz, 2H, C ar - H), 7.37 (d, J = 8.8 Hz, 2H, C ar - H), 7.29 (d, J = 8.7 Hz, 2H, C ar - H), (m, 5H, C ar - H), 6.80 (d, J = 7.2 Hz, 2H, C ar - H), 4.37 (d, J = 12.5 Hz, 1H, CH), 3.84 (d, J = 12.5 Hz, 1H, CH), 3.46 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 128.6(C ar - H), (C ar - H), (C ar - H), 81.5 (Cq), 77.4 (Cq), 59.8 (CH), 54.1 (CH). I.R. (thin film) ν 3494, 1761, 1721, 1493, 1400, 1279, 1181, 1140, 1092, 1014, 906, 818, 786, 736, 697 cm - 1. HRMS (ESI) for C 24 H [(M- H)- H] - : calcd , found Product 3o : C 24 H MW: g.mol -1 H C 25 H 21 4 MW: g.mol -1 General procedure using 3- chloro- 3- (m- methoxy)phenyl- 1- phenylpropane- 1,2- dione 1g (57.7 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96 :4) gave 3o as a yellow oil. Yield : 95% (80.1 mg, 0.19 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.79 min, t 2 = min. [α] 22 D = (c= 0.33 in CH 3, 90% ee). 1 H NMR (CD 3, 400 MHz) δ 9.80 (d, J = 1.8 Hz, 1H, aldehyde), 7.61 (d, J = 7.2 Hz, 2H, C ar - H), 7.50 (t, J = 7.4 Hz, 2H, C ar - H), 7.46 (t, J = 7.0 Hz, 1H, C ar - H), 7.33 (t, J = 8.0 Hz, 1H, C ar - H), (m, 3H, C ar - H), (m, 5H, C ar - H), 4.55 (d, J = 12.5 Hz, 1H, CH), 3.98 (dd, J = 1.5, 12.5 Hz, 1H, CH), 3.77 (s, 3H, CH 3 ), 3.35 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), 129.1(C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.9 (Cq), 77.6 (Cq), 60.1 (CH), 55.5 (CH 3 ), 14

15 53.9 (CH). I.R. (thin film) n 3363, 1762, 1723, 1601, 1493, 1451, 1279, 1173, 1139, 1054, 907, 730, 691 cm - 1. HRMS (ESI) for C 25 H 21 4 [(M- H)- H] - : calcd , found Product 3p : H C 25 H 21 3 MW: g.mol -1 General procedure using 3- chloro- 3- (p- methyl)phenyl- 1- phenylpropane- 1,2- dione 1h (54.5 mg, 0.2 mmol), cinnamaldehyde 2a (52.8 mg, 0.4 mmol) and the diarylprolinol silylether catalyst II (24 mg, 0.04 mmol) in Toluene (0.4 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 96:4) gave 3p as a yellow solid. Yield : 80% (64.9 mg, 0.16 mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.91 min, t 2 = min. [α] 22 D = (c= 0.60 in CH 3, 90% ee). 1 H NMR (CD 3, 400 MHz) δ 9.81 (s, 1H, aldehyde), 7.65(d, J = 7.1 Hz, 2H, C ar - H), (m, 3H, C ar - H), (m, 7H, C ar - H), 6.93 (d, J = 7.2 Hz, 2H, C ar - H), 4.58 (d, J = 12.1 Hz, 1H, CH), 4.02 (d, J = 12.5 Hz, 1H, CH), 3.41 (s, 1H, H), 2.45 (s, 3H, CH 3 ). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (C ar - H), (C ar - H), (C ar - H), 129.1(C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.8 (Cq), 77.7 (Cq), 60.1 (CH), 53.9 (CH), 21.3 (CH 3 ). I.R. (thin film) ν 3457, 1758, 1727, 1497, 1450, 1279, 1140, 1063, 759, 693, 613 cm - 1. Mp C. HRMS (ESI) for C 25 H 21 3 [(M- H)- H] - : calcd , found Product 3q : H C 24 H 18 N 5 MW: g.mol -1 N 2 General procedure using 3- chloro- 3- (p- nitro)phenyl- 1- phenylpropane- 1,2- dione 1i (30.4 mg, 0.1 mmol), cinnamaldehyde 2a (26.4 mg, 0.2 mmol) and the diarylprolinol silylether catalyst II (12 mg, 0.02 mmol) in Toluene (0.2 ml). Purification by flash chromatography (c- hexane/etac 100:1 - > 98 :2 - > 90:10) gave 3q as a yellow solid. Yield : 69% (30 mg, 69 µmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : The enantiomeric excess was determined by chiral SFC Chiralpak AY- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 9.51 min, t 2 = min. [α] 22 D = (c= 0.34 in CH 3, 77% ee). 1 H NMR (CD 3, 400 MHz) δ 9.80 (d, J = 1.3 Hz, 1H, aldehyde), 8.26 (d, J = 8.8 Hz, 2H, C ar - H), 7.61 (d, J = 7.3 Hz, 2H, C ar - H), (m, 5H, C ar - H), (m, 3H, C ar - H), 6.87 (d, J = 7.4 Hz, 2H, C ar - H), 4.51 (d, J = 12.4 Hz, 1H, CH), 4.04 (d, J = 12.4 Hz, 1H, CH), 3.47 (s, 1H, H). 13 C NMR (CD 3, 100 MHz) δ (ketone Cq), (aldehyde CH), (Cq), (Cq), 138.6(Cq), (Cq), (C ar - H), (C ar - H), 129.2(C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 81.6 (Cq), 77.5 (Cq), 60.0 (CH), 54.1 (CH). I.R. (thin film) ν 3457, 1761, 1723, 1603, 1521, 1450, 1348, 1279, 1137, 1058, 906, 853, 793, 728, 695, 608 cm - 1. Mp C. HRMS (ESI) for C 24 H 18 N 5 [(M- H)- H] - : calcd , found

16 IV. Procedure for the synthesis of 3-fluoro-1,3-diphenylpropane- 1,2-dione 5: F DMP F H CH 2 2, rt, 4h 9 5 To a well- stirred mixture of 3- fluoro- 2- hydroxy- 1,3- diphenylpropan- 1- one 9 (368 mg, 1.51 mmol, 1.0 equiv.) in anhydrous CH 2 2 (9.2 ml) was added Dess- Martin periodinane (767 mg, 1.81 mmol, 1.2 equiv.) portionwise as a solid. The resultant yellow solution was stirred at ambient temperature under an inert atmosphere for 4 h (apparition of a cloudy precipitate). The mixture was poured into 10% (w/w) aqueous Na 2 S 2 3 and extracted twice with methylene chloride. The combined organic layers were washed with water, then brine, dried over anhydrous Na 2 S 4, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (c- hexane/etac 98:2), affording a yellow crystalline solid. Yield : 70% (254 mg, 1.07 mmol). R f (silica gel, c- Hex/EtAc 95:5) H NMR (CD 3, 400 MHz) δ 7.85 (dd, J = 1.2, 8.2 Hz, 2H, C ar - H), 7.60 (t, J = 7.5 Hz, 1H, C ar - H), (m, 7H, C ar - H), 6.63 (d, J H- F = 46.9 Hz, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (d, J C- F = 25.7 Hz, ketone Cq), (ketone Cq), (C ar - H), (Cq), (d, J C- F = 20.3 Hz, Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), 59.3 (d, J C- F = Hz, CH). 19 F NMR (376 MHz, CD 3 ) δ (s, 1F, CH- F). I.R. (thin film) ν 1740, 1677, 1596, 1448, 1283, 1252, 1190, 1123, 1036, 932, 816, 790, 702, 666 cm - 1. Mp C. HRMS (ESI) for C 15 H 11 F 2 [M- H] - : calcd , found V. Procedure for the organocatalytic domino Michael/aldol reaction of 3-fluoro-1,3-diphenylpropane-1,2-dione 5 to cinnamaldehyde: F N H Ph Ph TMS 20 mol% Toluene, rt, 30min F 5 2a 6 16

17 To a solution of cinnamaldehyde 2a (26.4 mg, 0.2 mmol, 2.0 equiv.) in Toluene (0.2 ml) are added successively Hayashi- Jorgensen catalyst I (6.5 mg, 0.02 mmol, 20 mol%) and 3- fluoro- 1,3- diphenylpropane- 1,2- dione 5 (24.2 mg, 0.1 mmol1.0 equiv.). The mixture was stirred at room temperature for 30 minutes. Then mixture was quenched with 1 ml of 1M H solution and extracted three times with 5 ml of CH 2 2. The combined organic layers were dried over anhydrous Na 2 S 4, filtered and concentrated under reduced pressure. The crude product was purified by preparative TLC plate (c- hexane/etac 8 :2), affording the corresponding cyclopentanone 6. Yield : 68% (24.3 mg, mmol). dr >20 :1 (determined by 1 H NMR of the crude reactive mixture). R f (silica gel, c- Hex/EtAc 9:1) : 0.4. The enantiomeric excess was determined by chiral SFC Chiralpak AS- 3, 10% Isopropanol- 1%/min- 25% Isopropanol in C 2, 30 C, t 1 = 8.31 min, t 2 = 9.03 min. [α] 22 D = (c= 0.32 in CH 3, 90% ee). 1 H NMR (CD 3, 400 MHz) δ (s, 1H, aldehyde), (m, 2H, C ar - H), (m, 3H, C ar - H), (m, 3H, C ar - H), (m, 3H, C ar - H), (m, 2H, C ar - H), (m, 2H, C ar - H), 4.80 (d, J H- F = 22.4 Hz, 1H, CH). 13 C NMR (CD 3, 100 MHz) δ (d, J C- F = 14.5 Hz, ketone Cq), (aldehyde CH), (Cq), (Cq), (Cq), (Cq), (d, J C- F = 18.6 Hz, Cq), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (C ar - H), (d, J C- F = 6.7 Hz, C ar - H), 98.7 (d, J C- F = 147.1Hz, Cq), 55.9 (d, J C- F = 23.1 Hz, CH). 19 F NMR (376 MHz, CD 3 ) δ (s, 1F, C- F). I.R. (thin film) ν 1725, 1673, 1448, 1247, 1203, 1110, 980, 996, 770, 745, 697, 626 cm - 1. Mp C. HRMS (ESI) for C 24 H 17 F 2 [M- H] - : calcd , found References : 1) Xu, W.; Zhou, Y.; Wang, R.; Wu, G.; Chen, P. rg. Biomol. Chem. 2012, 10, ) Harwood, L. M.; Moody, C. J. Experimental rganic Chemistry, Principles and Practice, John Wiley and Sons, 1989, ) Battistuzzi, G.; Cacchi, S.; Fabrizi, G. rg. Lett. 2003, 5, ) Cresswell, A. J.; Davies, S. G.; Lee J. A.; Roberts, P. M.; Russell, A. J.; Thomson, J. E.; Tyte, M. J. rg. Lett, 2010, 12, ) Marques, C. S.; Moura, N. M. M.; Burke, A. J.; Furtado,. R. Tetrahedron Lett. 2007, 48,

18 H 3a C 24 H 19 3 MW: g.mol -1 18

19 H 3b C 25 H 21 4 MW: g.mol -1 19

20 H 3c C 25 H 21 4 MW: g.mol -1 20

21 H 3d C 25 H 21 3 MW: g.mol -1 21

22 H 3e C 25 H 21 4 MW: g.mol -1 22

23 H 3f F C 24 H 18 F 3 MW: g.mol -1 23

24 H Br 3g C 24 H 18 Br 3 MW: g.mol -1 24

25 H Br 3h C 24 H 18 Br 3 MW: g.mol -1 25

26 H C 22 H 17 4 MW: g.mol -1 3i 26

27 H 3j C 24 H MW: g.mol -1 27

28 Br H 3k C 24 H 18 Br 3 MW: g.mol -1 28

29 H 3l C 25 H 21 4 MW: g.mol -1 29

30 H 3m C 25 H 21 3 MW: g.mol -1 30

31 H 3n C 24 H MW: g.mol -1 31

32 H 3o C 25 H 21 4 MW: g.mol -1 32

33 H 3p C 25 H 21 3 MW: g.mol -1 33

34 H N 2 3q C 24 H 18 N 5 MW: g.mol -1 34

35 F 6 C 24 H 17 F 2 MW: g.mol -1 35

36 C 15 H 11 2 MW: g.mo l-1 1a 1H NMR 400 MHz, CD3 36

37 13C NMR 100 MHz, CD3 37

38 1b 1 H NMR 300 MHz, CD3 C 15 H MW:

39 13 C NMR 75 MHz, CD 3 39

40 Br C 15 H 10 Br 2 MW: c H NMR 400 MHz, CD3 40

41 13 C NMR 100 MHz, CD 3 41

42 Me C 16 H 13 3 MW: d H NMR 300 MHz, CD3 42

43 13 C NMR 75 MHz, CD 3 43

44 1 1e H NMR 300 MHz, CD3 C 16 H 13 2 MW:

45 13 C NMR 75 MHz, CD 3 45

46 1 1f H NMR 400 MHz, CD3 C 15 H MW:

47 13 C NMR 100 MHz, CD 3 47

48 C 16 H 13 3 MW: Me 1g 1 H NMR 300 MHz, CD3 48

49 13 C NMR 75 MHz, CD 3 49

50 1h 1 H NMR 400 MHz, CD3 C 16 H 13 2 MW:

51 13 C NMR 100 MHz, CD 3 51

52 N 2 1i 1 H NMR 400 MHz, CD3 C 15 H 10 N 4 MW:

53 13 C NMR 100 MHz, CD 3 53

54 Br 1j 1 H NMR 400 MHz, CD3 C 15 H 10 Br 2 MW:

55 13 C NMR 100 MHz, CD 3 55

56 1 1k H NMR 400 MHz, CD3 C 16 H 13 2 MW:

57 13 C NMR 100 MHz, CD 3 57

58 H 1 3a H NMR 400 MHz, CD3 C 24 H 19 3 MW: g.mol -1 58

59 13 C NMR 100 MHz, CD 3 59

60 H 1 3b H NMR 300 MHz, CD3 C 25 H 21 4 MW: g.mol -1 60

61 13 C NMR 100 MHz, CD 3 61

62 H 1 3c H NMR 400 MHz, CD3 C 25 H 21 4 MW: g.mol -1 62

63 13 C NMR 100 MHz, CD 3 63

64 H 1 3d H NMR 400 MHz, CD3 C 25 H 21 3 MW: g.mol -1 64

65 13 C NMR 100 MHz, CD 3 65

66 H 1 3e H NMR 400 MHz, CD3 C 25 H 21 4 MW: g.mol -1 66

67 13 C NMR 100 MHz, CD 3 67

68 H 1 3f H NMR 400 MHz, CD3 F C 24 H 18 F 3 MW: g.mol -1 68

69 13 C NMR 100 MHz, CD 3 69

70 H Br 1 3g H NMR 400 MHz, CD3 C 24 H 18 Br 3 MW: g.mol -1 70

71 13 C NMR 100 MHz, CD 3 71

72 H Br 1 3h H NMR 400 MHz, CD3 C 24 H 18 Br 3 MW: g.mol -1 72

73 13 C NMR 100 MHz, CD 3 73

74 H C 22 H 17 4 MW: g.mol -1 3i 74

75 13 C NMR 100 MHz, CD 3 75

76 H 1 3j H NMR 400 MHz, CD3 C 24 H MW: g.mol -1 76

77 13 C NMR 100 MHz, CD 3 77

78 Br H 3k 1 H NMR 400 MHz, CD3 C 24 H 18 Br 3 MW: g.mol -1 78

79 13 C NMR 100 MHz, CD 3 79

80 H 1 3l H NMR 400 MHz, CD3 C 25 H 21 4 MW: g.mol -1 80

81 13 C NMR 100 MHz, CD 3 81

82 H 1 3m H NMR 400 MHz, CD3 C 25 H 21 3 MW: g.mol -1 82

83 13 C NMR 100 MHz, CD 3 83

84 H 1 3n H NMR 400 MHz, CD3 C 24 H MW: g.mol -1 84

85 13 C NMR 100 MHz, CD 3 85

86 H 3o 1 H NMR 400 MHz, CD3 C 25 H 21 4 MW: g.mol -1 86

87 13 C NMR 100 MHz, CD 3 87

88 H 3p 1 H NMR 400 MHz, CD3 C 25 H 21 3 MW: g.mol -1 88

89 13 C NMR 100 MHz, CD 3 89

90 H N 2 1 3q H NMR 400 MHz, CD3 C 24 H 18 N 5 MW: g.mol -1 90

91 13 C NMR 100 MHz, CD 3 91

92 F 5 1 H NMR 400 MHz, CD3 C 15 H 11 F 2 MW: g.mol -1 92

93 13 C NMR 100 MHz, CD 3 93

94 19 F NMR 376 MHz, CD 3 94

95 F C 24 H 17 F 2 MW: g.mol H NMR 400 MHz, CD3 95

96 13 C NMR 100 MHz, CD 3 96

97 19 F NMR 376 MHz, CD 3 97

98 Crystal Structure Determination: Compound (3k) X- ray data were measured using Cu radiation on a SuperNova Dual source equipped with an Atlas detector. The crystal was kept at 190 K during data collection. Refinement was made within the ShelXL [1] refinement package using Least Squares minimisation. Hydrogen atom positions were calculated geometrically and constrained to ride on the parent atom during the refinement. The crystal structure has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number: CCDC Table 1. Crystal data and structure refinement for al03_725_abs. Identification code Empirical formula al03_725_abs C28 H28 Br 4 Formula weight Temperature Wavelength Crystal system 180(2) K Å Monoclinic Space group P 2 1 Unit cell dimensions a = (14) Å a= 90. b = (12) Å b= (19). c = (16) Å g = 90. Volume (3) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm - 1 F(000) 560 Crystal size x x mm 3 Theta range for data collection 4.90 to

99 Index ranges - 12<=h<=12, - 17<=k<=17, - 12<=l<=10 Reflections collected Independent reflections 5059 [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full- matrix least- squares on F 2 Data / restraints / parameters 5059 / 1 / 313 Goodness- of- fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.000(11) Largest diff. peak and hole and e.å - 3 Table 2. Bond lengths [Å] and angles [ ] for al03_725_abs. Br(1)- C(10) (19) (1)- C(3) (19) (1)- C(2) 1.203(3) (2)- C(1) 1.426(2) (2)- H(2) 0.72(4) (3)- C(6) 1.182(3) C(1)- C(7) 1.509(2) C(1)- C(5) 1.543(3) 99

100 C(1)- C(2) 1.544(3) C(2)- C(3) 1.543(3) C(3)- C(19) 1.503(3) C(3)- C(4) 1.550(3) C(4)- C(13) 1.514(3) C(4)- C(5) 1.540(3) C(4)- H(4) C(5)- C(6) 1.519(3) C(5)- H(5) C(6)- H(6) C(7)- C(8) 1.387(3) C(7)- C(12) 1.397(3) C(8)- C(9) 1.390(3) C(8)- H(8) C(9)- C(10) 1.379(3) C(9)- H(9) C(10)- C(11) 1.377(3) C(11)- C(12) 1.379(3) C(11)- H(11) C(12)- H(12) C(13)- C(14) 1.388(3) C(13)- C(18) 1.388(3) C(14)- C(15) 1.389(4) C(14)- H(14) C(15)- C(16) 1.376(4) 100

101 C(15)- H(15) C(16)- C(17) 1.376(4) C(16)- H(16) C(17)- C(18) 1.389(3) C(17)- H(17) C(18)- H(18) C(19)- C(20) 1.384(3) C(19)- C(24) 1.394(3) C(20)- C(21) 1.395(4) C(20)- H(20) C(21)- C(22) 1.372(5) C(21)- H(21) C(22)- C(23) 1.374(5) C(22)- H(22) C(23)- C(24) 1.385(4) C(23)- H(23) C(24)- H(24) (1S)- C(2S) 1.426(6) (1S)- C(4S) 1.448(6) C(2S)- C(3S) 1.242(10) C(2S)- H(2SA) C(2S)- H(2SB) C(3S)- H(3SA) C(3S)- H(3SB) C(3S)- H(3SC)

102 C(4S)- C(5S) 1.423(8) C(4S)- H(4SA) C(4S)- H(4SB) C(5S)- H(5SA) C(5S)- H(5SB) C(5S)- H(5SC) C(1)- (2)- H(2) 112(3) (2)- C(1)- C(7) (14) (2)- C(1)- C(5) (17) C(7)- C(1)- C(5) (19) (2)- C(1)- C(2) (17) C(7)- C(1)- C(2) (18) C(5)- C(1)- C(2) (14) (1)- C(2)- C(3) 125.3(2) (1)- C(2)- C(1) 125.0(2) C(3)- C(2)- C(1) (17) C(19)- C(3)- C(2) (16) C(19)- C(3)- C(4) (16) C(2)- C(3)- C(4) (16) C(19)- C(3)- (1) (14) C(2)- C(3)- (1) (13) C(4)- C(3)- (1) (13) C(13)- C(4)- C(5) (17) C(13)- C(4)- C(3) (16) 102

103 C(5)- C(4)- C(3) (16) C(13)- C(4)- H(4) C(5)- C(4)- H(4) C(3)- C(4)- H(4) C(6)- C(5)- C(4) (18) C(6)- C(5)- C(1) (18) C(4)- C(5)- C(1) (16) C(6)- C(5)- H(5) C(4)- C(5)- H(5) C(1)- C(5)- H(5) (3)- C(6)- C(5) 123.7(2) (3)- C(6)- H(6) C(5)- C(6)- H(6) C(8)- C(7)- C(12) (18) C(8)- C(7)- C(1) (17) C(12)- C(7)- C(1) (17) C(7)- C(8)- C(9) (19) C(7)- C(8)- H(8) C(9)- C(8)- H(8) C(10)- C(9)- C(8) (19) C(10)- C(9)- H(9) C(8)- C(9)- H(9) C(11)- C(10)- C(9) (19) C(11)- C(10)- Br(1) (16) C(9)- C(10)- Br(1) (15) 103

104 C(10)- C(11)- C(12) 119.1(2) C(10)- C(11)- H(11) C(12)- C(11)- H(11) C(11)- C(12)- C(7) 121.0(2) C(11)- C(12)- H(12) C(7)- C(12)- H(12) C(14)- C(13)- C(18) 117.8(2) C(14)- C(13)- C(4) 122.8(2) C(18)- C(13)- C(4) 119.4(2) C(13)- C(14)- C(15) 121.2(3) C(13)- C(14)- H(14) C(15)- C(14)- H(14) C(16)- C(15)- C(14) 120.2(3) C(16)- C(15)- H(15) C(14)- C(15)- H(15) C(15)- C(16)- C(17) 119.3(2) C(15)- C(16)- H(16) C(17)- C(16)- H(16) C(16)- C(17)- C(18) 120.4(2) C(16)- C(17)- H(17) C(18)- C(17)- H(17) C(13)- C(18)- C(17) 121.0(2) C(13)- C(18)- H(18) C(17)- C(18)- H(18) C(20)- C(19)- C(24) 118.4(2) 104

105 C(20)- C(19)- C(3) 124.3(2) C(24)- C(19)- C(3) (19) C(19)- C(20)- C(21) 120.0(3) C(19)- C(20)- H(20) C(21)- C(20)- H(20) C(22)- C(21)- C(20) 120.9(3) C(22)- C(21)- H(21) C(20)- C(21)- H(21) C(21)- C(22)- C(23) 119.6(3) C(21)- C(22)- H(22) C(23)- C(22)- H(22) C(22)- C(23)- C(24) 120.1(3) C(22)- C(23)- H(23) C(24)- C(23)- H(23) C(23)- C(24)- C(19) 121.0(2) C(23)- C(24)- H(24) C(19)- C(24)- H(24) C(2S)- (1S)- C(4S) 106.3(5) C(3S)- C(2S)- (1S) 118.8(7) C(3S)- C(2S)- H(2SA) (1S)- C(2S)- H(2SA) C(3S)- C(2S)- H(2SB) (1S)- C(2S)- H(2SB) H(2SA)- C(2S)- H(2SB) C(2S)- C(3S)- H(3SA)

106 C(2S)- C(3S)- H(3SB) H(3SA)- C(3S)- H(3SB) C(2S)- C(3S)- H(3SC) H(3SA)- C(3S)- H(3SC) H(3SB)- C(3S)- H(3SC) C(5S)- C(4S)- (1S) 110.6(3) C(5S)- C(4S)- H(4SA) (1S)- C(4S)- H(4SA) C(5S)- C(4S)- H(4SB) (1S)- C(4S)- H(4SB) H(4SA)- C(4S)- H(4SB) C(4S)- C(5S)- H(5SA) C(4S)- C(5S)- H(5SB) H(5SA)- C(5S)- H(5SB) C(4S)- C(5S)- H(5SC) H(5SA)- C(5S)- H(5SC) H(5SB)- C(5S)- H(5SC) Symmetry transformations used to generate equivalent atoms: Table 3. Hydrogen bonds for al03_725_abs [Å and ]. D- H...A d(d- H) d(h...a) d(d...a) <(DHA) (2)- H(2)...(1S)#1 0.72(4) 2.07(4) 2.739(3) 155(4) 106

107 Symmetry transformations used to generate equivalent atoms: #1 - x+1,y- 1/2,- z+1 Figure 1- rtep view of Al03_725 (50% probability level). Ether solvate molecule is omitted for clarity. Remarque: There is one hydrogen bond between the Et2 solvate molecule and the H group of the compound (see table 3 and figure 2). 107

108 Figure