An Enantioselective Oxidative C H/C H Cross-Coupling Reaction: Highly Efficient Method to Prepare Planar Chiral Ferrocenes

Supporting Information for An Enantioselective Oxidative C H/C H Cross-Coupling Reaction: Highly Efficient Method to Prepare Planar Chiral Ferrocenes De-Wei Gao, Qing Gu, and Shu-Li You* State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China Fax (+86) 21-54925087; E-mail: slyou@sioc.ac.cn Table of Contents General methods General procedure for the synthesis of substrates (1a-i) Complete optimization data S2 S2 S6 General procedure for the enantioselective synthesis of planar chiral ferrocene derivatives S9 Synthesis of planar chiral catalysts or ligands and their applications in asymmetric reactions X-Ray crystal structures of (R p )-3zh and 3zk References Copies of NMR spectra and HPLC chromatographs S30 S33 S36 S38 S1

General methods. Unless stated otherwise, all solvents were purified and dried according to standard methods prior to use. 1 H and 19 F NMR spectra were recorded on Varian or Agilent instrument (400 MHz and 376 MHz, 300 MHz and 282 MHz, respectively) and referenced relative to tetramethylsilane signal or residual protio solvent signals and CFCl 3 respectively. 13 C NMR spectra were recorded on Varian or Agilent instrument (100 MHz or 75 MHz) and referenced relative to residual solvent signals. Data for 1 H NMR are recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet or unresolved, br = broad singlet, coupling constant(s) in Hz, integration). Data for 13 C NMR and 19 F NMR are reported in terms of chemical shift (δ, ppm). General procedure for the synthesis of substrates (1a-i) Compounds 1a-d [1-3] were prepared by reductive amination of ferrocene aldehyde with the corresponding amines. 1-Dimethylaminomethyl-1 -bromoferrocene was synthesized according to known literature [4]. Dimethylaminomethylferrocene (1a) Analytical data for 1a [1] : 1 H NMR (400 MHz, CDCl 3 ) δ 4.14 (t, J = 1.6 Hz, 2H), 4.08 (s, 7H), 3.25 (s, 2H), 2.14 (s, 6H). Pyrrolidin-1-ylmethylferrocene (1b) Analytical data for 1b [2] : 1 H NMR (400 MHz, CDCl 3 ) δ 4.18 (t, J = 0.9 Hz, 2H), 4.10 (m, 5H), 4.09 (s, 2H), 3.42 (s, 2H), 2.45 (t, J = 6.3 Hz, 4H), 1.71 (t, J = 4.4 Hz, 4H). S2

Piperidin-1-ylmethylferrocene (1c) Analytical data for 1c [3] : 1 H NMR (400 MHz, CDCl 3 ) δ 4.14 (t, J = 1.6 Hz, 2H), 4.09-4.08 (m, 7H), 3.34 (s, 2H), 3.31 (s, 4H), 1.54-1.48 (m, 4H), 1.34 (t, J = 4.4 Hz, 2H). Methylpropylaminomethylferrocene (1d) Analytical data for 1d [3] : 1 H NMR (400 MHz, CDCl 3 ) δ 4.16 (s, 2H), 4.11 (s, 7H), 3.39 (s, 2H), 2.25 (s, 2H), 2.15 (s, 3H), 1.55-1.42 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H). Procedure A: To a solution of 1,1 -dibromoferrocene (5.58 g, 30 mmol, 1 equiv.) in hexane (100 ml) at 0 o C was successively added TMEDA (3.49 g, 30 mmol, 1 equiv.) and n BuLi (25.2 ml, 63 mmol, 2.1 equiv.). The reaction mixture was stirred at room temperature for 19 h. Then DMF (6.58 g, 90 mmol, 3 equiv.) was added dropwise. After that, the mixture was warmed to room temperature and stirred overnight. The reaction mixture was quenched with ice-cold water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na 2 SO 4 and filtrated. After the solvent was removed under reduced pressure, the crude aldehyde was obtained and used directly in the next step. To a solution of the above obtained aldehyde (2.3 g, 9.5 mmol, 1.0 equiv.) in S3

methanol (30 ml) were added triethylamine (1.35 g, 13.3 mmol, 1.4 equiv.), 4Å MS (400 mg) and dimethylamine hydrochloride (0.85 g, 10.5 mmol, 1.1 equiv.). Then sodium cyanoborohydride (0.78 g, 12.35 mmol, 1.3 equiv.) was added. The mixture was stirred overnight. Then the reaction mixture was filtrated through a pad of celite. After the solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate/petroleum = 1/4 to 2:1, v/v) to give 1e (0.78 g, 17.7% yield). Analytical data for 1e [5] : 1 H NMR (400 MHz, CDCl 3 ) δ 9.87 (s, 1H), 4.68 (d, J = 1.6 Hz, 2H), 4.51 (d, J = 1.2 Hz, 2H), 4.22 (d, J = 1.2 Hz, 2H), 4.18 (d, J = 1.6 Hz, 2H), 3.12 (s, 2H), 2.10 (s, 6H). To a solution of 1-dimethylaminomethyl-1 -bromoferrocene (1 equiv.) in tetrahydrofuran (0.2 mol/l) at -78 o C was added n BuLi (1.1 equiv.). The reaction mixture was stirred at -78 o C for 2.5 h. Then the corresponding electrophile reagent (1.5 equiv.) was added dropwise. After that, the mixture was warmed to room temperature and stirred overnight. The reaction mixture was quenched with ice-cold water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na 2 SO 4 and filtrated. After the solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate/petroleum = 1/10, v/v) to give 1f-i. 1-Dimethylaminomethyl-1 -(2-hydroxypropan-2-yl)ferrocene (1f) Yellow solid (0.26 g, 22% yield). Analytical data for 1f: m.p. = 55.3-57.6 o C. 1 H NMR (400 MHz, CDCl 3 ) δ 4.20 (t, J = 1.6 Hz, 2H), 4.14 (t, J = 2.0 Hz, 2H), 4.10-4.09 (m, 4H), 3.26 (s, 2H), 2.26 (s, 6H), 1.48 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 100.8, 84.5, 69.8, 68.4, 68.1, 68.0, 66.2, 58.6, 45.3, 31.3. IR (film) 3346, 3096, 2976, 2933, S4

2757, 1465, 1370, 1348, 1166, 1127, 836, 798, 757 cm -1. HRMS (ESI) calcd for C 16 H 24 56 FeNO [M+H] + : 302.1202, Found: 302.1203. 1-Dimethylaminomethyl-1 -(2-hydroxydiphenylmethyl)ferrocene (1g) Yellow solid (1.14 g, 54% yield). Analytical data for 1g: m.p. = 147.8-150.0 o C. 1 HNMR (300 MHz, CDCl 3 ) δ 7.31-7.19 (m, 10H), 4.53 (br, 1H), 4.21 (s, 2H), 4.15 (s, 2H), 4.04 (s, 2H), 4.00 (s, 2H), 2.95 (s, 2H), 2.20 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.5, 127.5, 127.0, 126.7, 98.8, 84.9, 77.4, 70.3, 69.2, 68.8, 68.2, 58.2, 45.4. IR (film) 3351, 3078, 2977, 2941, 1450, 1040, 750, 705 cm -1. HRMS (ESI) calcd for C 26 H 56 28 FeNO [M+H] + : 426.1515, Found: 426.1513. 1-Dimethylaminomethyl-1 -trimethylsilylferrocene (1h) Red oil (0.16 g, 78% yield). Analytical data for 1h: 1 H NMR (400 MHz, CDCl 3 ) δ 4.24 (t, J = 1.6 Hz, 2H), 4.12 (t, J = 1.6 Hz, 2H), 4.05 (t, J = 2.0 Hz, 2H), 4.00 (t, J = 1.6 Hz, 2H), 3.25 (s, 2H), 2.14 (s, 6H), 0.21 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 83.2, 73.3, 72.2, 71.4, 70.2, 68.3, 59.2, 44.7, -0.2. IR (film) 3088, 2950, 2765, 1455, 1247, 1163, 1036, 901, 825, 752, 691, 630 cm -1. HRMS (ESI) calcd for C 16 H 56 26 FeNSi [M+H] + : 316.1178, Found: 316.1177. 1-Dimethylaminomethyl-1 -diphenylphosphorylferrocene (1i) Yellow solid (0.74 g, 59% yield). Analytical data for 1i: m.p. = 110.9-112.7 o C. 1 H NMR (300 MHz, CDCl 3 ) δ 7.69-7.63 (m, 4H), 7.52-7.40 (m, 6H), 4.42 (d, J = 1.5 Hz, 2H), 4.29 (d, J = 1.8 Hz, 2H), 4.26 (s, 2H), 4.16 (d, J = 1.8 Hz, 2H), 3.20 (br, 1H), S5

3.06 (s, 2H), 2.11 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 134.3 (d, J = 105.5 Hz), 131.5 (d, J = 2.7 Hz), 131.4 (d, J = 9.9 Hz), 128.2 (d, J = 11.8 Hz), 84.3, 73.0 (d, J = 116.6 Hz), 72.7 (d, J = 12.5 Hz), 72.2 (d, J = 10.2 Hz), 71.8, 69.8, 58.1, 44.5. 31 P NMR (121 MHz, CDCl 3 ) δ 29.1. IR (film) 3076, 2947, 2927, 2773, 1437, 1204, 1167, 1021, 721, 698 cm -1. HRMS (ESI) calcd for C 25 H 56 27 FeNOP [M+H] + : 444.1174, Found: 444.1175. Complete optimization data Table S1. Examination of ligand a entry ligand yield (%) b ee (%) c 1 d Boc-L-Val-OH 44 99 2 Boc-L-Val-OH 48 98 3 Boc-L-Phe-OH 45 94 4 Boc-L-Ile-OH 53 98 5 Boc-L-Nva-OH 48 94 6 Boc-L-Pro-OH 15 0 7 Boc-L-Leu-OH 53 94 8 Boc-L-Abu-OH 51 93 9 Boc-L-Ala-OH 43 89 10 Boc-L-Met-OH <10 nd 11 Ac-L-Ile-OH 46 87 12 Cbz-L-Ile-OH 48 95 13 Fmoc-L-Ile-OH trace nd a Reaction conditions: 1a (0.3 mmol), benzofuran (0.45 mmol), Pd(OAc) 2 (10 mol %), ligand (20 mol %), K 2 CO 3 (0.3 mmol) in DMA under air at 80 C unless noted otherwise. b Isolated yield. c Determined by HPLC analysis. d At 70 C. S6

Table S2. Examination of base a entry base yield (%) b ee (%) c 1 K 2 CO 3 53 98 2 Cs 2 CO 3 9 97 3 Na 2 CO 3 12 78 4 NaOAc 12 45 5 KHCO 3 40 93 6 KOAc 26 67 7 K 3 PO 4 35 90 8 CsOAc 42 84 9 KF 10 62 10 d K 2 CO 3 54 98 11 e K 2 CO 3 53 98 a Reaction conditions: 1a (0.3 mmol), benzofuran (0.45 mmol), Pd(OAc) 2 (10 mol %), Boc-L-Ile-OH (20 mol %), base (0.3 mmol) in DMA under air at 80 C unless noted otherwise. b Isolated yield. c Determined by HPLC analysis. d with K 2 CO 3 (1.5 equiv.). e with K 2 CO 3 (2.0 equiv.). Table S3. Examination of solvent a entry solvent yield (%) b ee (%) c 1 DMA 54 98 2 DMF 54 98 S7

3 NMP 17 96 4 DMSO 12 99 5 DCM <10 nd 6 THF <10 nd 7 p-xylene 24 75 a Reaction conditions: 1a (0.3 mmol), benzofuran (0.45 mmol), Pd(OAc) 2 (10 mol %), Boc-L-Ile-OH (20 mol %), K 2 CO 3 (0.3 mmol) in solvent under air at 80 C unless noted otherwise. b Isolated yield. c Determined by HPLC analysis. Table S4. Examination the loading of bezofuran a entry benzofuran (equiv.) yield (%) b ee (%) c 1 1.5 54 98 2 2.0 60 99 3 3.0 61 99 4 4.0 65 99 a Reaction conditions: 1a (0.3 mmol), benzofuran, Pd(OAc) 2 (10 mol %), Boc-L-Ile-OH (20 mol %), K 2 CO 3 (0.3 mmol) in DMF under air at 80 C unless noted otherwise. b Isolated yield. c Determined by HPLC analysis. Table S5. Examination of additive a entry additive yield (%) b ee (%) c 1-60 99 S8

2 d BQ 65 99 3 e DMBQ 62 99 4 f DDQ 22 95 5 g BQ 54 98 6 h BQ 35 98 7 i BQ 71 99 a Reaction conditions: 1a (0.3 mmol), benzofuran (0.6 mmol), Pd(OAc) 2 (10 mol %), Boc-L-Ile-OH (20 mol %), K 2 CO 3 (0.3 mmol) in DMF under air at 80 C unless noted otherwise. b Isolated yield. c Determined by HPLC analysis. d Benzoquinone (10 mol %). e 2,6-dimethylbenzoquinone (10 mol %). f 2,3-dichloro-5,6-cyanobenzoquinone (10 mol %). g Benzoquinone (0.5 equiv.). h Benzoquinone (1.0 equiv.). i Benzoquinone (10 mol %) and water (4.0 equiv.). General procedure for the enantioselective synthesis of planar chiral ferrocene derivatives To a solution of Pd(OAc) 2 (6.7 mg, 0.03 mmol, 0.1 equiv.), Boc-L-Ile-OH (13.9 mg, 0.06 mmol, 0.2 equiv.), K 2 CO 3 (62.2 mg, 0.45 mmol, 1.5 equiv.), 1,4-benzoquinone (3.2 mg, 0.03 mmol, 0.1 equiv.) in DMA (2.0 ml) were added ferrocene 1 (0.3 mmol, 1.0 equiv.), heteroarenes 2 (0.6 mmol, 2.0 equiv.) and water (21.6 mg, 1.2 mmol, 4.0 equiv.) successively. The mixture was stirred at 80 o C under air (open flask). After the reaction was complete (monitored by TLC), it was then quenched with saturated aqueous K 2 CO 3 solution and extracted with EtOAc three times. The combined organic layers were washed with H 2 O and brine successively, then dried over anhydrous Na 2 SO 4 and filtrated. After the solvent was removed under reduced pressure, the residue was purified by column chromatography (ethyl acetate/ S9

petroleum ether = 1/15 to 1/2, v/v, 2% Et 3 N) to afford the desired product 3. (R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)ferrocene (3a) Red oil (76.5 mg, 71% yield, 99% ee). Analytical data for 3a: [α] 20 D = +299.3 (c = 1.0 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.57-7.52 (m, 2H), 7.30-7.22 (m, 2H), 6.86 (s, 1H), 4.80 (s, 1H), 4.38 (s, 1H), 4.33 (s, 1H), 4.11 (s, 5H), 4.03 (AB, J AB = 12.8 Hz, 1H), 3.26 (BA, J BA = 12.8 Hz, 1H), 2.28 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.6, 154.5, 129.6, 123.3, 122.7, 120.2, 110.8, 102.1, 82.3, 75.5, 72.7, 70.1, 68.2, 68.1, 58.3, 45.1. IR (film): 2965, 2934, 2814, 2764, 1601, 1456, 1257, 811, 740, 683 cm -1. HRMS (ESI) calcd for C 21 H 56 22 FeNO [M+H] + : 360.1045, Found: 360.1045. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 18.317 min, t (major) = 20.623 min. (R p )-1-(Pyrrolidin-1-ylmethyl)-2-(bezofuran-2-yl)ferrocene (3b) Red oil (85.6 mg, 74% yield, 98% ee). Analytical data for 3b: [α] 20 D = +402.5 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.56-7.50 (m, 2H), 7.29-7.21 (m, 2H), 6.84 (s, 1H), 4.77 (d, J = 1.6 Hz, 1H), 4.41(d, J = 1.6 Hz, 1H), 4.31 (t, J = 2.0 Hz, 1H), 4.20 (AB, J AB = 12.8 Hz, 1H), 4.11 (s, 5H), 3.47 (BA, J BA = 12.4 Hz, 1H), 2.56 (d, J = 5.2 Hz, 4H), 1.75 (m, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.7, 154.5, 129.6, 123.2, 122.7, 120.1, 110.8, 102.1, 83.0, 75.1, 72.2, 70.0, 68.1, 67.9, 54.2, 53.7, 23.4. IR (film): 3095, 2938, 2855, 2814, 2765, 1574, 1455, 1020, 1006, 808, 783 cm -1. HRMS (ESI) calcd for C 23 H 56 24 FeNO [M+H] + : 386.1202, Found: 386.1200. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 3 N = 98 / 2/ 0.5, 0.3 ml/min, λ = 230 nm, t (minor) = 16.240 min, t (major) = 17.182 min. S10

(R p )-1-(Piperidin-1-ylmethyl)-2-(bezofuran-2-yl)ferrocene (3c) Red oil (83.4 mg, 70% yield, 98% ee). Analytical data for 3c: [α] 20 D = +435.9 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.54-7.48 (m, 2H), 7.27-7.19 (m, 2H), 6.88 (s, 1H), 4.75 (s, 1H), 4.36 (s, 1H), 4.29 (s, 1H), 4.08 (s, 5H), 3.99 (AB, J AB = 12.8 Hz, 1H), 3.36 (BA, J BA = 13.2 Hz, 1H), 2.43-2.36 (m, 4H), 1.54-1.52 (m, 4H), 1.387-1.378 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.7, 154.5, 129.6, 123.2, 122.6, 120.1, 110.7, 102.3, 82.1, 75.7, 72.8, 70.0, 68.0, 67.9, 57.7, 53.9, 26.0, 24.4. IR (film): 2987, 2969, 2901, 2883, 1261, 1066, 802 cm -1. HRMS (ESI) calcd for C 24 H 56 26 FeNO [M+H] + : 400.1358, Found: 400.1359. The enantiomeric excess was determined by Daicel Chiralpak AD-H (0.46 cm x 25 cm), Hexanes / IPA / Et 2 NH = 95 / 5 / 0.1, 0.7 ml/min, λ = 254 nm, t (major) = 3.80 min, t (minor) = 4.29 min. (R p )-1-Methylpropylaminomethyl-2-(bezofuran-2-yl)ferrocene (3d) Red oil (79.0 mg, 68% yield, 99% ee). Analytical data for 3d: [α] 20 D = +404.5 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.56-7.50 (m, 2H), 7.30-7.21 (m, 2H), 6.91 (s, 1H), 4.78 (t, J = 2.0 Hz, 1H), 4.39 (t, J = 2.4 Hz, 1H), 4.32 (t, J = 2.4 Hz, 1H), 4.12 (s, 5H), 4.07 (AB, J AB = 12.8 Hz, 1H), 3.35 (BA, J BA = 12.8 Hz, 1H), 2.44-2.34 (m, 2H), 2.19 (s, 3H), 1.62-1.49 (m, 2H), 0.94 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.7, 154.5, 129.6, 123.2, 122.6, 120.1, 110.8, 102.3, 82.7, 75.6, 72.8, 70.1, 68.1, 68.0, 59.5, 56.7, 41.5, 20.5, 12.0. IR (film): 3095, 2959, 2934, 2784, 1603, 1456, 1257, 1105, 1001, 809, 740 cm -1. HRMS (ESI) calcd for C 23 H 56 26 FeNO [M+H] + : 388.1358, Found: 388.1360. The enantiomeric excess was determined by Daicel Chiralpak AD-H (0.46 cm x 25 cm), Hexanes / IPA / Et 2 NH = 98 / 2 / 0.1, 0.7 ml/min, λ = 254 nm, t (major) = 3.90 min, t (minor) = 4.46 min. S11

(R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)-1 -formylferrocene (3e) Red oil (46.0 mg, 40% yield, 97% ee). Analytical data for 3e: [α] 20 D = +517.7 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 9.81 (s, 1H), 7.55-7.53 (m, 1H), 7.49 (dd, J = 8.0, 0.4 Hz, 1H), 7.30-7.26 (m, 1H), 7.24-7.20 (m, 1H), 6.88 (s, 1H), 4.87 (dd, J = 2.4, 2.0 Hz, 1H), 4.70-4.69 (m, 2H), 4.51-4.48 (m, 2H), 4.45 (dd, J = 2.4, 1.6 Hz, 1H), 4.41 (t, J = 2.8 Hz, 1H), 3.89 (AB, J AB = 12.8 Hz, 1H), 3.12 (BA, J BA = 13.2 Hz, 1H), 2.24 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 193.4, 154.6, 154.2, 129.2, 123.9, 122.9, 120.6, 110.8, 103.4, 83.9, 80.4, 75.3, 75.1, 73.8, 71.3, 71.1, 69.4, 69.4, 57.5, 46.1, 45.1. IR (film): 3104, 2941, 2858, 2816, 2766, 2713, 1680, 1455, 1243, 1171, 1021, 990, 827, 741 cm -1. HRMS (ESI) calcd for C 22 H 56 22 FeNO 2 [M+H] + : 388.0994, Found: 388.0996. The enantiomeric excess was determined by Daicel Chiralpak IA (0.46 cm x 25 cm), Hexanes / IPA / Et 2 NH = 80 / 20 / 0.1, 0.7 ml/min, λ = 254 nm, t (major) = 7.87 min, t (minor) = 8.89 min. (R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)-1 -(2-hydroxypropan-2-yl)ferrocene (3f) Red oil (91.7 mg, 73% yield, 98% ee). Analytical data for 3f: [α] D 20 = +284.4 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.51-7.47 (m, 2H), 7.26-7.17 (m, 2H), 6.78 (s, 1H), 4.80 (s, 1H), 4.45 (s, 1H), 4.32 (s, 1H), 4.08 (s, 2H), 4.02 (s, 1H), 3.95 (s, 1H), 3.79 (AB, J AB = 13.2 Hz, 1H), 3.43 (BA, J BA = 13.6 Hz, 1H), 3.25 (br, 1H), 2.32 (s, 6H), 1.43 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 155.8, 154.3, 129.3, 123.6, 122.9, 120.2, 110.8, 102.3, 101.6, 83.2, 75.2, 72.2, 70.6, 70.2, 68.5, 68.1, 67.8, 67.3, 67.1, 58.3, 45.7, 31.6, 31.0. IR (film): 3564, 3428, 2975, 2934, 2859, 2816, 2768, 1602, 1456, 1257, 1168, 831, 749 cm -1. HRMS (ESI) calcd for C 24 H 28 56 FeNO 2 S12

[M+H] + : 418.1464, Found: 418.1466. The enantiomeric excess was determined by phenomenex cellulose-2 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 6.537 min, t (major) = 8.615 min. (R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)-1 -(hydroxydiphenylmethyl)ferroce ne (3g) Foamy red solid (89.3 mg, 55% yield, 99% ee). Analytical data for 3g: m.p. = 57.2-60.3 o C. [α] D 20 = +242.6 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.49 (t, J = 8.0 Hz, 2H), 7.31 (m, 12H), 6.71 (s, 1H), 4.76 (d, J = 1.6 Hz, 1H), 4.33 (s, 1H), 4.22 (t, J = 1.6 Hz, 1H), 4.07 (t, J = 2.4 Hz, 1H), 4.02 (m, 3H), 3.69 (AB, J AB = 13.6 Hz, 1H), 3.24 (BA, J BA = 13.6 Hz, 1H), 2.32 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 155.6, 154.4, 147.4, 147.3, 129.3, 127.6, 127.5, 127.0, 126.9, 126.8, 126.7, 123.6, 122.9, 120.2, 110.9, 102.5, 99.0, 77.5, 75.6, 72.6, 72.0, 70.9, 70.5, 69.5, 68.5, 68.2, 57.9, 45.7. IR (film): 3547, 3083, 2924, 2768, 1600, 1455, 1257, 1017, 748, 699 cm -1. HRMS (ESI) calcd for C 34 H 32 56 FeNO 2 [M+H] + : 542.1777, Found: 542.1781. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 37.833 min, t (major) = 55.466 min. (R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)-1 -(trimethylsilyl)ferrocene (3h) Red oil (106.8 mg, 82% yield, 97% ee). Analytical data for 3h: [α] 20 D = +201.0 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.54-7.48 (m, 2H), 7.28-7.19 (m, 2H), 6.82 (s, 1H), 4.76 (s, 1H), 4.35 (s, 1H), 4.27 (t, J = 2.8 Hz, 1H), 4.19-4.16 (m, 2H), 4.07-4.04 (m, 2H), 4.02 (AB, J AB = 13.2 Hz, 1H), 3.25 (BA, J BA = 12.8 Hz, 1H), 2.25 (s, 6H), 0.24 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.4, 154.5, 129.5, 123.3, 122.7, 120.2, 110.7, 102.1, 81.9, 75.4, 75.0, 74.1, 74.0, 73.8, 73.1, 72.9, 68.4, 68.4, S13

58.2, 45.0, -0.2. IR (film): 3086, 2950, 2814, 2764, 1603, 1456, 1247, 1163, 1035, 828, 740, 691 cm -1. HRMS (ESI) calcd for C 24 H 56 30 FeNOSi [M+H] + : 432.1441, Found: 432.1445. The enantiomeric excess was determined by Diacel Chiralcel OD-H (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 9.499 min, t (major) = 11.385 min. (R p )-1-Dimethylaminomethyl-2-(bezofuran-2-yl)-1 -(diphenylphosphoryl)ferrocene (3i) Foamy red solid (115.8 mg, 69% yield, 99% ee). Analytical data for 3i: m.p. = 57.1-60.3 o C. [α] D 20 = +233.5 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.64-7.63 (m, 4H), 7.47-7.41 (m, 8H),7.23-7.18 (m, 2H), 6.74 (s, 1H), 4.78 (s, 1H), 4.57 (s, 1H), 4.42-4.33 (m, 4H), 4.23 (s, 1H), 3.94 (AB, J AB = 12.0 Hz, 1H), 3.19 (BA, J BA = 11.6 Hz, 1H), 2.20 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 154.9, 154.5, 134.6, 134.5, 133.6, 133.4, 131.7, 131.6, 131.5,131.4, 131.4, 131.2, 129.2, 128.4, 128.3, 128.3, 128.3, 128.2, 123.7, 122.9, 121.0, 120.4, 110.8, 103.1, 82.1, 77.3, 76.9, 75.4, 75.3, 75.3, 74.7, 74.4, 74.4, 74.4, 74.3, 73.9, 73.9, 73.8, 73.8, 73.2, 70.4, 69.7, 56.9, 44.4. 31 P NMR (CDCl 3 161 MHz) δ 28.1. IR (film): 3667, 3521, 3429, 2933, 2855, 2816, 2767, 1456, 1436, 1165, 1117, 1024, 833, 748, 722, 699 cm -1. HRMS (ESI) calcd for C 33 H 31 56 FeNO 2 P [M+H] + : 560.1436, Found: 560.1437. The enantiomeric excess was determined by phenomenex cellulose-2 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 4.750 min, t (major) = 5.127 min. (R p )-1-Dimethylaminomethyl-2-(5-methylbenzofuran-2-yl)ferrocene (3j) Red oil (73.7 mg, 66% yield, 97% ee). Analytical data for 3j: [α] D 20 = +15.2 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.38 (d, J = 8.4 Hz, 1H), 7.33 (s, S14

1H), 7.08 (dd, J = 8.0, 1.2 Hz, 1H), 6.76 (d, J = 0.8 Hz, 1H), 4.77 (dd, J = 2.4, 1.6 Hz, 1H), 4.37 (d, J = 2.4, 1.6 Hz, 1H), 4.31 (t, J = 2.4 Hz, 1H), 4.10 (s, 5H), 4.00 (AB, J AB = 13.2 Hz, 1H), 3.27 (BA, J BA = 12.8 Hz, 1H), 2.46 (s, 3H), 2.26 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.6, 152.9, 132.0, 129.7, 124.4, 120.1, 110.2, 101.8, 82.2, 75.6, 72.6, 70.1, 68.1, 68.0, 58.2, 45.1, 21.4. IR (film): 2937, 2856, 2814, 2764, 1600, 1455, 1264, 1198, 988, 907, 797, 729 cm -1. HRMS (ESI) calcd for C 22 H 56 24 FeNO [M+H] + : 374.1202, Found: 374.1199. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 3 N = 95 / 5 / 0.1, 0.7 ml/min, λ = 254 nm, t (minor) = 7.457 min, t (major) = 8.218 min. (R p )-1-Dimethylaminomethyl-2-(5-methoxybenzofuran-2-yl)ferrocene (3k) Red oil (84.2 mg, 72% yield, 99% ee). Analytical data for 3k: [α] 20 D = +19.5 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.35 (d, J = 9.2 Hz, 1H), 6.98 (d, J = 2.8 Hz, 1H), 6.84 (dd, J = 8.8, 2.4 Hz, 1H), 6.75 (s, 1H), 4.74 (t, J = 1.2 Hz, 1H), 4.34 (t, J = 2.0 Hz, 1H), 4.29 (t, J = 2.4 Hz, 1H), 4.07 (s, 5H), 3.97 (AB, J AB = 12.8 Hz, 1H), 3.84 (s, 3H), 3.22 (BA, J BA = 12.8 Hz, 1H), 2.23 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.4, 155.9, 149.5, 130.1, 111.6, 111.1, 102.8, 102.2, 82.2, 75.5, 72.6, 70.0, 68.0, 68.0, 58.2, 55.9, 45.1. IR (film): 3094, 2934, 2854, 2814, 2764, 1600, 1480, 1449, 1415, 1241, 1207, 1031, 991, 807, 750 cm -1. HRMS (ESI) calcd for C 22 H 56 24 FeNO 2 [M+H] + : 390.1151, Found: 390.1149. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 2 NH = 90 / 10 / 0.1, 0.7 ml/min, λ = 254 nm, t (minor) = 7.41 min, t (major) = 8.00 min. (R p )-1-Dimethylaminomethyl-2-(5-isopropylbenzofuran-2-yl)ferrocene (3l) Red oil (82.3 mg, 68% yield, 99% ee). Analytical data for 3l: [α] 20 D = +23.0 (c = 0.1 Acetone, 99% ee). 1 H NMR (300 MHz, CDCl 3 ) δ 7.45-7.41 (m, 2H), 7.16 (dd, J = 8.4, S15

1.8 Hz, 1H), 6.81 (s, 1H), 4.78 (s, 1H), 4.39 (s, 1H), 4.33 (t, J = 2.4 Hz, 1H), 4.12 (s, 5H), 4.02 (AB, J AB = 12.9 Hz, 1H), 3.29 (BA, J BA = 12.9 Hz, 1H), 3.11-2.98 (h, J = 6.6 Hz,1H), 2.27 (s, 6H), 1.35 (d, J = 6.6 Hz, 6H). 13 C NMR (75 MHz, CDCl 3 ) δ 156.4, 152.9, 143.2, 129.4, 122.0, 117.2, 110.2, 102.0, 82.0, 75.5, 72.4, 69.9, 67.89, 67.86, 58.0, 44.9, 34.0, 24.51, 24.48. IR (film): 3095, 2957, 2858, 2813, 2765, 1456, 1263, 989, 908, 806, 730 cm -1. HRMS (ESI) calcd for C 24 H 56 28 FeNO [M+H] + : 402.1515, Found: 402.1513. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 12.247 min, t (major) = 14.268 min. (R p )-1-Dimethylaminomethyl-2-(5-phenylbenzofuran-2-yl)ferrocene (3m) Red oil (100.2 mg, 77% yield, 99% ee). Analytical data for 3m: [α] 20 D = +16.2 (c = 0.1 Choloroform, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.74 (d, J = 1.2 Hz, 1H), 7.67-7.65 (m, 2H), 7.56 (d, J = 8.8 Hz, 1H), 7.51-7.45 (m, 3H), 7.36 (t, J = 7.2 Hz, 1H), 6.88 (s, 1H), 4.81 (t, J = 1.6 Hz, 1H), 4.40 (t, J = 2.4 Hz, 1H), 4.34 (t, J = 2.4 Hz, 1H), 4.12 (s, 5H), 4.03 (AB, J AB = 12.8 Hz, 1H), 3.28 (BA, J BA = 12.8 Hz, 1H), 2.28 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.4, 154.2, 141.9, 136.4, 130.1, 128.7, 127.5, 126.8, 123.0, 118.7, 110.8, 102.2, 82.3, 75.3, 72.7, 70.1, 68.18, 68.15, 58.2, 45.1. IR (film): 2935, 2856, 2814, 2765, 1600, 1468, 1265, 988, 811, 760, 696, 629 cm -1. HRMS (ESI) calcd for C 27 H 56 26 FeNO [M+H] + : 436.1358, Found: 436.1356. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 19.088 min, t (major) = 25.578 min. (R p )-1-Dimethylaminomethyl-2-(5-fluorobenzofuran-2-yl)ferrocene (3n) Red oil (55.0 mg, 49% yield, 99% ee). Analytical data for 3n: [α] D 20 = +28.3 (c = 0.1 S16

Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.39 (dd, J = 8.4, 3.6 Hz, 1H), 7.17 (dd, J = 8.8, 2.4 Hz, 1H), 6.96 (td, J = 11.6, 2.8 Hz, 1H), 6.80 (s, 1H), 4.77 (s, 1H), 4.38 (s, 1H), 4.33 (s, 1H), 4.09 (s, 5H), 3.99 (AB, J AB = 13.2 Hz, 1H), 3.23 (BA, J BA = 12.8 Hz, 1H), 2.25 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 159.3 (d, J = 236.0 Hz), 158.6, 150.7, 130.4 (d, J = 10.7 Hz), 111.1 (d, J = 9.1 Hz), 110.6 (d, J = 26.5 Hz), 105.6 (d, J = 25.1 Hz), 102.1 (d, J = 3.8 Hz), 82.3, 74.9, 72.9, 70.1, 68.3, 68.2, 58.2, 45.0. 19 F NMR (376 MHz, CDCl 3 ) δ -121.6. IR (film): 3096, 2936, 2856, 2815, 2765, 1600, 1475, 1447, 1184, 1128, 991, 850, 810, 766 cm -1. HRMS (ESI) calcd for C 21 H 21 F 56 FeNO [M+H] + : 378.0951, Found: 378.0949. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 15.717 min, t (major) = 17.237 min. (R p )-1-Dimethylaminomethyl-2-(5-chlorobenzofuran-2-yl)ferrocene (3o) Red oil (60.0 mg, 51% yield, 99% ee). Analytical data for 3o: [α] 20 D = +25.4 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.48 (d, J = 2.0 Hz, 1H), 7.39 (d, J = 8.8 Hz, 1H), 7.20 (dd, J = 8.8, 2.0 Hz, 1H), 6.78 (s, 1H), 4.77 (s, 1H), 4.38 (s, 1H), 4.33 (t, J = 2.4 Hz, 1H), 4.09 (s, 5H), 3.97 (AB, J AB = 12.8 Hz, 1H), 3.21 (BA, J BA = 12.8 Hz, 1H), 2.25 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.4, 152.9, 131.0, 128.2, 123.3, 119.7, 111.6, 101.5, 82.5, 74.7, 72.9, 70.1, 68.3, 68.2, 58.3, 45.1. IR (film): 3095, 2937, 2856, 2814, 2765, 1598, 1455, 1259, 1166, 989, 799, 731, 696 cm -1. HRMS (ESI) calcd for C 21 H 21 Cl 56 FeNO [M+H] + : 394.0656, Found: 394.0654. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 15.714 min, t (major) = 17.000 min. S17

(R p )-1-Dimethylaminomethyl-2-(5,7-dimethylbenzofuran-2-yl)ferrocene (3p) Red oil (77.7 mg, 67% yield, 99% ee). Analytical data for 3p: [α] 20 D = +24.1 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.16 (s, 1H), 6.90 (s, 1H), 6.71 (s, 1H), 4.76 (t, J = 2.0 Hz, 1H), 4.38 (t, J = 2.0 Hz, 1H), 4.32 (t, J = 2.4 Hz, 1H), 4.10 (s, 5H), 4.07 (AB, J AB = 12.8 Hz, 1H), 3.33 (BA, J BA = 12.8 Hz, 1H), 2.57 (s, 3H), 2.43 (s, 3H), 2.26 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.3, 152.0, 132.1, 129.0, 125.6, 120.3, 117.5, 102.0, 82.1, 75.8, 72.4, 70.1, 68.2, 68.0, 58.0, 45.0, 21.3, 15.1. IR (film): 2923, 2853, 2809, 2765, 1120, 1105, 987, 847, 815, 751 cm -1. HRMS (ESI) calcd for C 23 H 56 26 FeNO [M+H] + : 388.1358, Found: 388.1356. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 15.222 min, t (major) = 15.859 min. (R p )-1-Dimethylaminomethyl-2-(7-tert-butylbenzofuran-2-yl)ferrocene (3q) Red oil (79.8 mg, 64% yield, 98% ee). Analytical data for 3q: [α] 20 D = +23.7 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.40 (dd, J = 6.8, 2.0 Hz, 1H), 7.20-7.14 (m, 2H), 6.80 (s, 1H), 4.78 (dd, J = 2.0, 1.2 Hz, 1H), 4.39 (dd, J = 2.4, 2.0 Hz, 1H), 4.33 (t, J = 2.8 Hz, 1H), 4.10 (s, 5H), 4.05 (AB, J AB = 12.8 Hz, 1H), 3.32 (BA, J BA = 12.4 Hz, 1H), 2.45 (s, 6H), 1.62 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 155.3, 152.7, 134.2, 130.0, 122.6, 120.1, 118.3, 102.1, 82.1, 75.7, 72.5, 70.0, 68.3, 68.0, 58.0, 45.0, 34.3, 30.0. IR (film): 2954, 2868, 2813, 2764, 1407, 1168, 1019, 993, 807, 744 cm -1. HRMS (ESI) calcd for C 25 H 56 30 FeNO [M+H] + : 416.1671, Found: 416.1672. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 3 N= 95 / 5 / 0.1, 0.7 ml/min, λ = 254 nm, t (minor) = 5.948 min, t (major) = 6.273 min. (R p )-1-Dimethylaminomethyl-2-(7-chlorobezofuran-2-yl)ferrocene (3r) S18

Red oil (67.0 mg, 57% yield, 99% ee). Analytical data for 3r: [α] 20 D = +403.9 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.41 (d, J = 7.6 Hz, 1H), 7.25 (d, J = 7.6 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), 6.82 (s, 1H), 4.81 (s, 1H), 4.40 (s, 1H), 4.35 (s, 1H), 4.11 (s, 5H), 4.09 (AB, J AB = 12.8 Hz, 1H), 3.25 (BA, J BA = 12.8 Hz, 1H), 2.27 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.9, 150.3, 131.1, 123.6, 123.3, 118.6, 116.2, 102.1, 82.6, 74.5, 72.9, 70.2, 68.4, 68.3, 58.2, 45.1. IR (film): 3093, 2931, 2855, 2815, 2766, 1603, 1414, 805, 755, 732 cm -1. HRMS (ESI) calcd for C 21 H 21 Cl 56 FeNO [M+H] + : 394.0656, Found: 394.0663. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 15.207 min, t (major) = 17.202 min. (R p )-1-Dimethylaminomethyl-2-(5-methylfuran-2-yl)ferrocene (3s) Red oil (34.7 mg, 36% yield, 95% ee). Analytical data for 3s: [α] 20 D = +300.7 (c = 0.1 Acetone, 95% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 6.27 (d, J = 2.8 Hz, 1H), 5.94-5.93 (m, 1H), 4.54 (dd, J = 2.4, 1.6 Hz, 1H), 4.25 (t, J = 2.4 Hz, 1H), 4.18 (t, J = 2.4 Hz, 1H), 4.05 (s, 5H), 3.86 (AB, J AB = 12.8 Hz, 1H), 3.21 (BA, J BA = 12.8 Hz, 1H), 2.33 (s, 3H), 2.20 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 151.1, 150.5, 106.9, 106.6, 81.0, 71.4, 69.8, 67.2, 66.9, 58.0, 45.0, 13.8. IR (film): 3094, 2962, 2777, 1601, 1456, 1257, 1106, 807, 738 cm -1. HRMS (ESI) calcd for C 18 H 56 22 FeNO [M+H] + : 324.1045, Found: 324.1044. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 2 NH = 95 / 5 / 0.1, 0.7 ml/min, λ = 254 nm, t (minor) = 6.22 min, t (major) = 6.64 min. (R p )-1-Dimethylaminomethyl-2-(4,5-dimethylfuran-2-yl)ferrocene (3t) Red oil (50.3 mg, 50% yield, 97% ee). Analytical data for 3t: [α] 20 D = +276.0 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 6.15 (s, 1H), 4.52 (t, J = 2.0 Hz, S19

1H), 4.24 (t, J = 1.6 Hz, 1H), 4.17 (t, J = 2.4 Hz, 1H), 4.05 (s, 5H), 3.87 (AB, J AB = 12.8 Hz, 1H), 3.22 (BA, J BA = 12.8 Hz, 1H), 2.22 (s, 3H), 2.20 (s, 6H), 1.95 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 149.7, 145.8, 115.2, 109.1, 80.7, 77.5, 71.3, 69.8, 67.1, 66.8, 57.9, 45.0, 11.5, 10.0. IR (film): 3095, 2922, 2813, 2763, 1635, 1584, 1455, 1106, 1008, 807, 624 cm -1. HRMS (ESI) calcd for C 19 H 56 24 FeNO [M+H] + : 338.1202, Found: 338.1203. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA / Et 3 N = 98 / 2 / 0.1, 0.5 ml/min, λ = 254 nm, t (minor) = 13.623 min, t (major) = 14.432 min. (R p )-1-Dimethylaminomethyl-2-(5-acetylfuran-2-yl)ferrocene (3u) Red oil (66.3 mg, 63% yield, 99% ee). Analytical data for 3u: [α] 20 D = +67.8 (c = 0.1 Chloroform, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.15 (d, J = 3.6 Hz, 1H), 6.53 (d, J = 4.0 Hz, 1H) 4.72 (s, 1H), 4.34 (s, 1H), 4.29 (s, 1H), 4.05 (s, 5H), 3.90 (AB, J AB = 12.8 Hz, 1H), 3.16 (BA, J BA = 12.8 Hz, 1H), 2.47 (s, 3H), 2.19 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 185.7, 159.4, 151.2, 119.6, 108.1, 82.6, 73.9, 73.0, 70.2, 68.5, 68.2, 58.2, 45.1, 25.9. IR (film): 3095, 2939, 2856, 2815, 2766, 1665, 1522, 1412, 1290, 1105, 1022, 1004, 810 cm -1. HRMS (ESI) calcd for C 19 H 56 22 FeNO 2 [M+H] + : 352.0994, Found: 352.0993. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 95 / 5, 1.0 ml/min, λ = 254 nm, t (minor) = 33.135 min, t (major) = 37.690 min. (R p )-1-Dimethylaminomethyl-2-(5-methoxycarbonylfuran-2-yl)ferrocene (3v) Red oil (83.6 mg, 76% yield, 99% ee). Analytical data for 3v: [α] 20 D = +524.6 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.13 (t, J = 2.0 Hz, 1H), 6.48 (t, J = 2.8 Hz, 1H) 4.71 (s, 1H), 4.30 (s, 1H), 4.26 (s, 1H), 4.03 (s, 5H), 3.92 (AB, J AB = 12.8 Hz, 1H), 3.86 (s, 3H), 3.13 (BA, J BA = 12.8 Hz, 1H), 2.20 (s, 6H). 13 C NMR (100 S20

MHz, CDCl 3 ) δ 159.2, 158.8, 142.5, 120.0, 107.4, 82.4, 74.2, 72.7, 70.1, 68.3, 68.0, 58.1, 51.6, 45.0. IR (film): 2928, 2855, 2816, 2766, 1713, 1537, 1304, 1136, 811, 758 cm -1. HRMS (ESI) calcd for C 19 H 56 22 FeNO 3 [M+H] + : 368.0944, Found: 368.0944. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 9.219 min, t (major) = 10.072 min. (R p )-1-Dimethylaminomethyl-2-(5-phenylfuran-2-yl)ferrocene (3w) Red oil (81.7 mg, 71% yield, 99% ee). Analytical data for 3w: [α] 20 D = +743.2 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 7.2 Hz, 1H), 6.65 (d, J = 3.2 Hz, 1H), 6.48 (d, J = 3.2 Hz, 1H), 4.66 (s, 1H), 4.32 (s, 1H), 4.26 (s, 1H), 4.08 (s, 5H), 3.99 (AB, J AB = 12.4 Hz, 1H), 3.31 (BA, J BA = 12.8 Hz, 1H), 2.23 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 153.1, 152.2, 131.1, 128.8, 126.9, 123.3, 107.9, 106.8, 81.2, 76.4, 71.9, 70.0, 67.7, 67.3, 58.0, 45.0. IR (film): 3092, 2929, 2765, 1596, 1552, 1456, 1105, 1020, 1000, 808, 755, 690 cm -1. HRMS (ESI) calcd for C 23 H 56 24 FeNO [M+H] + : 386.1202, Found: 386.1201. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 17.761 min, t (major) = 20.270 min. (R p )-1-Dimethylaminomethyl-2-(5-(4-methoxyphenyl)furan-2-yl)ferrocene (3x) Red oil (95.1 mg, 76% yield, 99% ee). Analytical data for 3x: [α] 20 D = +843.3 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.66 (d, J = 8.8 Hz, 1H), 6.97 (d, J = 8.8 Hz, 1H), 6.52 (d, J = 3.2 Hz, 1H), 6.46 (d, J = 3.2 Hz, 1H), 4.65 (d, J = 1.2 Hz, 1H), 4.32 (t, J = 2.0 Hz, 1H), 4.25 (t, J = 2.4 Hz, 1H), 4.08 (s, 5H), 3.99 (AB, J AB = 12.4 Hz, 1H), 3.85 (s, 3H), 3.31 (BA, J BA = 12.4 Hz, 1H), 2.23 (s, 6H). 13 C NMR (100 S21

MHz, CDCl 3 ) δ 158.8, 152.3, 152.4, 124.8, 124.3, 114.3, 107.9, 105.1, 81.1, 76.7, 71.8, 70.0, 67.6, 67.2, 58.0, 55.4, 45.0. IR (film): 3094, 2940, 2814, 2765, 1499, 1247, 1174, 1022, 829, 755, 614 cm -1. HRMS (ESI) calcd for C 24 H 56 26 FeNO 2 [M+H] + : 416.1307, Found: 416.1310. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 27.633 min, t (major) = 32.892 min. (R p )-1-Dimethylaminomethyl-2-(5-(4-acetylphenyl)furan-2-yl)ferrocene (3y) Red oil (105.7 mg, 82% yield, 99% ee). Analytical data for 3y: [α] 20 D = +999.1 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 8.01 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 6.80 (d, J = 3.2 Hz, 1H), 6.52 (d, J = 3.2 Hz, 1H), 4.69 (s, 1H), 4.38 (s, 1H), 4.30 (s, 1H), 4.09 (s, 5H), 4.02 (AB, J AB = 13.2 Hz, 1H), 3.36 (BA, J BA = 12.8 Hz, 1H), 2.62 (s, 3H), 2.25 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 197.3, 154.9, 151.0, 135.0, 135.0, 129.2, 123.0, 109.6, 108.4, 80.9, 75.7, 72.3, 70.1, 68.1, 67.6, 57.9, 44.8, 26.6. IR (film): 2935, 2814, 2766, 1677, 1596, 1567, 1262, 1020, 808, 751 cm -1. HRMS (ESI) calcd for C 25 H 56 26 FeNO 2 [M+H] + : 428.1307, Found: 428.1310. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 19.804 min, t (major) = 23.457 min. (R p )-1-Dimethylaminomethyl-2-(5-methylthiophen-2-yl)ferrocene (3z) Red oil (58.7 mg, 58% yield, 97% ee). Analytical data for 3z: [α] 20 D = +411.5 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 6.98 (d, J = 3.2 Hz, 1H), 6.58-6.57 (m, 1H), 4.44 (m, 1H), 4.27 (t, J = 1.2 Hz, 1H), 4.18 (t, J = 2.4 Hz, 1H), 4.06 (s, 5H), 3.79 (AB, J AB = 12.8 Hz, 1H), 3.17 (BA, J BA = 13.2 Hz, 1H), 2.45 (s, 3H), 2.19 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.6, 138.1, 125.3, 125.1, 82.0, 81.5, 71.4, 70.3, 69.3, S22

67.0, 57.9, 45.0, 15.3. IR (film): 3093, 2938, 2854, 2812, 2763, 1728, 1454, 1016, 1001, 806 cm -1. HRMS (ESI) calcd for C 18 H 56 22 FeNS [M+H] + : 340.0817, Found: 340.0818. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 13.233 min, t (major) = 14.720 min. (R p )-1-Dimethylaminomethyl-2-(5-formylthiophen-2-yl))ferrocene (3za) Red oil (67.8 mg, 64% yield, 98% ee). Analytical data for 3za: [α] 20 D = +926.8 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 9.85 (s, 1H), 7.60 (d, J = 4.0 Hz, 1H), 7.39 (d, J = 3.6 Hz, 1H), 4.65 (dd, J = 2.4, 1.6 Hz, 1H), 4.39 (dd, J = 2.8, 1.6 Hz, 1H), 4.34 (t, J = 2.4 Hz, 1H), 4.07 (s, 5H), 3.85 (AB, J AB = 12.8 Hz, 1H), 3.12 (BA, J BA = 12.8 Hz, 1H), 2.22 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 182.7, 155.2, 141.3, 137.4, 126.1, 83.1, 78.4, 73.3, 71.0, 70.6, 68.5, 58.2, 45.0. IR (film): 3092, 2936, 2855, 2814, 2767, 1658, 1477, 1410, 1229, 807, 669 cm -1. HRMS (ESI) calcd for C 18 H 56 20 FeNOS [M+H] + : 354.0610, Found: 354.0611. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 16.449 min, t (major) = 20.152 min. (R p )-1-Dimethylaminomethyl-2-(5-acetylthiophen-2-yl))ferrocene (3zb) Dark red soild (66.6 mg, 60% yield, 97% ee). Analytical data for 3zb: m.p. = 94.6-97.0 o C. [α] 20 D = +719.1 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.50 (d, J = 4.0 Hz, 1H), 7.27 (d, J = 3.6 Hz, 1H), 4.59 (s, 1H), 4.34 (s, 1H), 4.29 (t, J = 2.4 Hz, 1H), 4.05 (s, 5H), 3.81 (AB, J AB = 12.4 Hz, 1H), 3.10 (BA, J BA = 13.2 Hz, 1H), 2.52 (s, 3H), 2.19 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 190.6, 153.3, 141.8, 133.2, 126.0, 82.9, 78.9, 72.9, 70.8, 70.3, 68.1, 58.1, 45.0, 26.4. IR (film): 2924, 2853, 2760, 1640, 1472, 1409, 1290, 1277, 998, 827, 813 cm -1. HRMS (ESI) calcd for S23

C 19 H 22 56 FeNOS [M+H] + : 368.0766, Found: 368.0770. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 15.572 min, t (major) = 18.872 min. (R p )-1-Dimethylaminomethyl-2-(5-methoxycarbonylthiophen-2-yl))ferrocene (3zc) Dark red solid (85.5 mg, 74% yield, 99% ee). Analytical data for 3zc: m.p. = 69.3-70.5 o C. [α] 20 D = +713.3 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.63 (d, J = 3.6 Hz, 1H), 7.25 (d, J = 3.6 Hz, 1H), 4.58 (s, 1H), 4.34 (s, 1H), 4.28 (s, 1H), 4.06 (s, 5H), 3.88 (s, 3H), 3.81 (AB, J AB = 12.8 Hz, 1H), 3.13 (BA, J BA = 12.8 Hz, 1H), 2.20 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.9, 151.1, 133.9, 130.6, 125.8, 82.8, 79.1, 72.6, 70.8, 70.2, 68.0, 58.0, 52.1, 45.0. IR (film): 3095, 2948, 2931, 2815, 2763, 1703, 1482, 1285, 1259, 1095, 812, 750 cm -1. HRMS (ESI) calcd for C 19 H 56 22 FeNO 2 S [M+H] + : 384.0715, Found: 384.0716. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 7.668 min, t (major) = 8.808 min. (R p )-1-Dimethylaminomethyl-2-(5-phenylthiophen-2-yl)ferrocene (3zd) Red oil (103.2 mg, 86% yield, 98% ee). Analytical data for 3zd: [α] 20 D = +848.2 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.66-7.64 (m, 2H), 7.42-7.38 (m, 2H), 7.28 (t, J = 7.2 Hz, 1H), 7.24 (d, J = 4.0 Hz, 1H), 7.18 (d, J = 3.6 Hz, 1H), 4.56 (t, J = 2.4 Hz, 1H), 4.33 (t, J = 2.4 Hz, 1H), 4.26 (t, J = 2.8 Hz, 1H), 4.11 (s, 5H), 3.88 (AB, J AB = 13.2 Hz, 1H), 3.19 (BA, J BA = 13.2 Hz, 1H), 2.25 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.2, 142.2, 134.6, 128.9, 127.1, 126.4, 125.4, 123.1, 82.4, 80.8, 71.9, 70.5, 69.5, 67.4, 58.1, 45.1. IR (film): 2938, 2850, 2812, 2764, 1446, 1293, 1104, 1028, 1013, 1000, 819, 754, 693 cm -1. HRMS (ESI) calcd for C 23 H 56 24 FeNS [M+H] + : 402.0973, Found: 402.0974. The enantiomeric excess was determined by S24

phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 16.523 min, t (major) = 20.618 min. (R p )-1-Dimethylaminomethyl-2-(4-phenylthiophen-2-yl)ferrocene (3ze) Red oil (52.2 mg, 44% yield, 98% ee). Analytical data for 3ze: [α] 20 D = +181.8 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.62-7.59 (m, 3H), 7.40 (t, J = 7.2 Hz, 2H), 7.34 (d, J = 1.2 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.18 (d, J = 3.6 Hz, 1H), 4.55 (s, 1H), 4.32 (s, 1H), 4.24 (s, 1H), 4.10 (s, 5H), 3.87 (AB, J AB = 12.8 Hz, 1H), 3.19 (BA, J BA = 13.2 Hz, 1H), 2.24 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 143.1, 141.9, 136.0, 128.8, 127.0, 126.2, 124.7, 118.7, 82.4, 80.9, 71.8, 70.5, 69.6, 67.3, 58.0, 45.0. IR (film): 3093, 2928, 2852, 2813, 2766, 1601, 1509, 1453, 1260, 1106, 1017, 819, 731, 693 cm -1. HRMS (ESI) calcd for C 23 H 56 24 FeNS [M+H] + : 402.0973, Found: 402.0976. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA /Et 2 NH = 95 / 5 / 0.1, 0.7 ml/min, λ = 254 nm, t (minor) = 7.11 min, t (major) = 7.67 min. (R p )-1-Dimethylaminomethyl-2-(5-(4-methoxyphenyl)thiophen-2-yl)ferrocene (3zf) Red soild (95.7 mg, 76% yield, 97% ee). Analytical data for 3zf: m.p. = 89.2-91.6 o C. [α] 20 D = +727.1 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.55 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 2.8 Hz, 1H), 7.04 (d, J = 2.8 Hz, 1H), 6.92 (d, J = 8.4 Hz, 2 H), 4.53 (s, 1H), 4.30 (s, 1H), 4.23 (s, 1H), 4.09 (s, 5H), 3.85 (AB, J AB = 12.8 Hz, 1H), 3.83 (s, 3H), 3.17 (BA, J BA = 12.8 Hz, 1H), 2.23 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.9, 142.2, 141.0, 127.5, 126.7, 126.3, 122.0, 114.3, 82.4, 81.0, 71.8, 70.5, 69.4, 67.2, 58.1, 55.4, 45.1. IR (film): 2936, 2812, 2765, 1517, 1247, 1178, 1035, 818, 759 cm -1. HRMS (ESI) calcd for C 24 H 56 26 FeNOS [M+H] + : 432.1079, Found: 432.1081. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), S25

Hexanes / IPA = 99 / 1, 1.0 ml/min, λ = 254 nm, t (minor) = 8.912 min, t (major) = 10.982 min. (R p )-1-Dimethylaminomethyl-2-(5-(4-fulorophenyl)thiophen-2-yl)ferrocene (3zg) Red oil (103.0 mg, 80% yield, 97% ee). Analytical data for 3zg: [α] 20 D = +879.1 (c = 0.1 Acetone, 97% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.59-7.56 (m, 2H), 7.21 (d, J = 4.0 Hz, 1H), 7.10-7.06 (m, 3H), 4.54 (d, J = 1.6 Hz, 1H), 4.32 (d, J = 1.2 Hz, 1H), 4.25 (t, J = 2.4 Hz, 1H), 4.10 (s, 5H), 3.86 (AB, J AB = 13.2 Hz, 1H), 3.19 (BA, J BA = 12.4 Hz, 1H), 2.23 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.1 (d, J = 246.0 Hz), 142.1, 141.1, 130.9, 127.0 (d, J = 8.3 Hz), 126.4, 123.0, 115.8 (d, J = 22.0 Hz), 82.3, 80.7, 71.9, 70.5, 69.5, 67.4, 58.0, 45.0. 19 F NMR (376 MHz, CDCl 3 ) δ -115.1. IR (film): 2962, 2813, 2768, 1516, 1260, 1224, 1014, 798 cm -1. HRMS (ESI) calcd for C 23 H 23 F 56 FeNS [M+H] + : 420.0879, Found: 420.0880. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 40 / 1, 0.41 ml/min, λ = 254 nm, t (minor) = 14.987 min, t (major) = 20.073 min. (R p )-1-Dimethylaminomethyl-2-(5-(4-methoxyphenyl)thiophen-2-yl)ferrocene (3zh) Red solid (99.0 mg, 76% yield, 99% ee). Analytical data for 3zh: m.p. = 125.0-126.6 o C. [α] 20 D = +759.6 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.55 (d, J = 7.6 Hz, 2H), 7.36 (d, J = 7.2 Hz, 2H), 7.24 (s, 1H), 7.15 (s, 1H), 4.56 (s, 1H), 4.34 (s, 1H), 4.26 (s, 1H), 4.10 (s, 5H), 3.87 (AB, J AB = 12.8 Hz, 1H), 3.18 (BA, J BA = 12.8 Hz, 1H), 2.25 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.8, 140.8, 133.1, 132.7, 129.0, 126.6, 126.4, 123.5, 82.5, 80.5, 72.0, 70.6, 69.6, 67.4, 58.1, 45.1. IR (film): 2934, 2853, 2767, 1504, 1456, 1294, 1091, 1011, 812 cm -1. HRMS (ESI) calcd for C 23 H 23 Cl 56 FeNS [M+H] + : 436.0584, Found: 436.0585. The enantiomeric excess was S26

determined by phenomenex cellulose-2 (25 cm), Hexanes / IPA = 99 / 1, 1.0 ml/min, λ = 254 nm, t (minor) = 5.695 min, t (major) = 7.387 min. (R p )-1-Dimethylaminomethyl-2-(5-formyl-1-methyl-1H-pyrrol-2-yl)ferrocene (3zi) Red solid (80.2 mg, 76% yield, 99% ee). Analytical data for 3zi: m.p. = 99.3-102.5 o C. [α] 20 D = +704.3 (c = 0.1 Acetone, 99% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 9.47 (s, 1H), 6.93 (d, J = 4.0 Hz, 1H), 6.53 (d, J = 4.0 Hz, 1H), 4.42 (s, 1H), 4.35 (d, J = 2.4 Hz, 2H), 4.16 (s, 5H), 3.82 (s, 3H), 3.41 (AB, J AB = 12.8 Hz, 1H), 3.34 (BA, J BA = 12.8 Hz, 1H), 1.98 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.8, 140.7, 132.5, 124.0, 113.2, 84.3, 77.3, 71.2, 70.2, 69.7, 68.1, 56.7, 44.5, 33.7. IR (film): 2961, 2925, 2854, 2772, 1643, 1499, 1352, 1260, 1022, 816 cm -1. HRMS (ESI) calcd for C 19 H 56 23 FeN 2 O [M+H] + : 351.1154, Found: 351.1155. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 21.526 min, t (major) = 30.728 min. (R p )-1-Dimethylaminomethyl-2-(5-acetyl-1-methyl-1H-pyrrol-2-yl)ferrocene (3zj) Red oil (114.0 mg, 82% yield, 98% ee). Analytical data for 3zj: [α] 20 D = +358.4 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 6.97 (d, J = 3.6 Hz, 2H), 6.41 (d, J = 3.6 Hz, 1H), 4.40 (s, 1H), 4.31 (s, 2H), 4.13 (s, 5H), 3.74 (s, 3H), 3.37 (s, 2H), 2.41 (s, 3H), 1.95 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.9, 138.6, 131.3, 119.2, 111.7, 83.9, 78.2, 70.8, 70.1, 70.0, 67.9, 56.5, 44.3, 34.5, 27.2. IR (film): 3096, 2936, 2854, 2814, 2766, 1643, 1493, 1370, 1001, 941, 819, 771, 644 cm -1. HRMS (ESI) calcd for C 20 H 56 25 FeN 2 O [M+H] + : 365.1311, Found: 365.1312. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 18.701 min, t (major) = 26.449 min. S27

(R p )-1-Dimethylaminomethyl-2-(5-methoxycarbonyl-1-methyl-1H-pyrrol-2-yl)ferroce ne (3zk) Red oil (54.0 mg, 47% yield, 98% ee). Analytical data for 3zk: [α] 20 D = +222.9 (c = 0.1 Acetone, 98% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 6.99 (d, J = 4.0 Hz, 1H), 6.41 (d, J = 4.0 Hz, 1H), 4.40 (s, 1H), 4.33-4.31 (m, 2H), 4.15 (s, 5H), 3.80 (s, 3H), 3.73 (s, 3H), 3.37 (s, 2H), 1.96 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 161.7, 137.0, 122.6, 117.0, 111.6, 84.0, 78.8, 70.6, 70.1, 70.1, 67.8, 56.5, 51.0, 44.4, 33.7. IR (film): 3093, 2947, 2814, 2765, 1700, 1496, 1251, 1235, 1106, 1020, 803, 754 cm -1. HRMS (ESI) calcd for C 20 H 56 25 FeN 2 O 2 [M+H] + : 381.1260, Found: 381.1260. The enantiomeric excess was determined by phenomenex cellulose-4 (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (minor) = 9.790 min, t (major) = 10.889 min. (R p )-1-Dimethylaminomethyl-2-(5-(3-ethoxy-3-oxoprop-1-en-1-yl)-1-methyl-1H-pyrr ol-2-yl)ferrocene (3zl) Red oil (60.0 mg, 48% yield, 95% ee). Analytical data for 3zl: [α] 20 D = +574.3 (c = 0.1 Acetone, 95% ee). 1 H NMR (400 MHz, CDCl 3 ) δ 7.60 (d, J = 15.6 Hz, 1H), 6.71 (d, J = 4.0 Hz, 1H), 6.48 (d, J = 4.0 Hz, 1H), 6.15 (d, J = 15.6 Hz, 1H), 4.39 (t, J = 1.6 Hz, 1H), 4.30 (d, J = 2.0 Hz, 2H), 4.23 (q, J = 7.2 Hz, 2H), 4.15 (s, 5H), 3.53 (s, 3H), 3.40 (AB, J AB = 13.2 Hz, 1H), 3.33 (BA, J BA = 13.2 Hz, 1H), 1.98 (s, 6H), 1.32 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 168.0, 134.8, 132.7, 130.0, 112.9, 111.6, 111.3, 83.8, 79.2, 70.7, 70.1, 70.0, 67.6, 60.0, 56.7, 44.5, 31.6, 14.4. IR (film): 3096, 2976, 2939, 2814, 2766, 1696, 1613, 1151, 1037, 811, 753 cm -1. HRMS (ESI) calcd for C 23 H 56 29 FeN 2 O 2 [M+H] + : 421.1573, Found: 421.1575. The enantiomeric excess was determined by phenomenex cellulose-2 (25 cm), Hexanes / IPA = 90 / 10, 0.4 S28

ml/min, λ = 230 nm, t (major) = 36.873 min, t (minor) = 43.023 min. (R p )-1-Dimethylaminomethyl-2-(5-chloro-1-methyl-1H-indol-2-yl)ferrocene (3zm) Red oil (62.5 mg, 51% yield, 98% ee). Analytical data for 3zm: [α] 20 D = -55.1 (c = 0.1 Acetone, 98% ee). 1 H NMR (600 MHz, CDCl 3 ) δ 7.58 (d, J = 1.8 Hz, 1H), 7.17 (d, J = 9.0 Hz, 1H), 7.13 (dd, J = 8.4, 1.8 Hz, 1H), 6.71 (s, 1H), 4.46 (s, 1H), 4.38 (s, 1H), 4.36 (t, J = 2.4 Hz, 1H), 4.19 (s, 5H), 3.61 (s, 3H), 3.50 (AB, J AB = 12.6 Hz, 1H), 3.39 (BA, J BA = 13.2 Hz, 1H), 2.00 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 138.3, 136.1, 128.6, 125.2, 121.2, 119.4, 110.1, 103.4, 84.3, 78.8, 70.8, 70.2, 70.0, 67.9, 56.7, 44.6, 30.6. IR (film): 3096, 2967, 2815, 2767, 1470, 1106, 818, 790, 753 cm -1. HRMS (ESI) calcd for C 22 H 24 Cl 56 FeN 2 [M+H] + : 407.0972, Found: 407.0975. The enantiomeric excess was determined by Daicel Chiralcel OD-H (25 cm), Hexanes / IPA = 90 / 10, 1.0 ml/min, λ = 254 nm, t (major) = 18.994 min, t (minor) = 27.125 min. Note: the proposed C2 selectivity of indole was determined by NOE. (R p )-1-Dimethylaminomethyl-2-(5-methylbenzo[b]thiophen-2-yl)) (3zn 2 ) Red solid (86.3 mg, 74% yield, xx% ee). Analytical data for 3zn 2 : 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 (d, J = 8.0 Hz, 1H), 7.53 (s, 1H), 7.46 (d, J = 0.4 Hz, 1H), 7.14 (dd, J = 8.4, 1.2 Hz, 1H), 4.63 (dd, J = 2.0, 1.2 Hz, 1H), 4.37 (dd, J = 2.4, 1.2 Hz, 1H), 4.30 (t, J = 2.4 Hz, 1H), 4.12 (s, 5H), 3.93 (AB, J AB = 12.8 Hz, 1H), 3.19 (BA, J BA = 13.2 Hz, 1H), 2.48 (s, 3H), 2.28 (s, 6H). Note: 3zn 2 and 3zn 3 could not be purified by silica gel column chromatography. We gave the 1 H NMR spectra of the mixture. S29

Synthesis of planar chiral catalysts or ligands and their applications in asymmetric reactions To a solution of (R p )-1-dimethylaminomethyl-2-(bezofuran-2-yl)ferrocene 3a (1 equiv.) in diethyl ether (0.06 mol/l) at -78 o C was added t BuLi (1.5 equiv.). The reaction mixture was stirred at -78 o C for 5 h. Then the corresponding electrophile reagent (2.0 equiv.) (dissolved in diethyl ether, 0.2 mol/l) was added dropwise. After that, the mixture was warmed to room temperature and stirred overnight. The reaction mixture was quenched with ice-cold water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na 2 SO 4 and filtrated. After the solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate/petroleum = 1/20, v/v) to give 4. (R p )-1-(Bezofuran-2-yl)-2-dimethylaminomethyl-3-(hydroxydiphenylmethyl)ferrocen e (4a) Red solid (349.5 mg, 54% yield). Analytical data for 4a: m.p. = 164.5-166.0 o C. [α] D 20 = +260.9 (c = 0.1 Acetone). 1 H NMR (400 MHz, CDCl 3 ) δ 9.11 (br, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 7.6 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.35 (d, J = 7.6 Hz, 2H), 7.28-7.24 (m, 5H), 7.20 (t, J = 7.2 Hz, 2H), 7.14 (t, J = 7.2 Hz, 1H), 6.70 (s, 1H), 4.67 (d, J = 2.4 Hz, 1H), 4.02 (s, 5H), 4.00 (d, J = 2.4 Hz, 1H), 3.87 (AB, J AB = 13.6 Hz, 1H), 3.15 (BA, J BA = 13.6 Hz, 1H), 2.10 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.1, 154.5, 149.6, 147.2, 129.1, 127.5, 127.5, 127.5, 127.2, 126.5, 126.5, 123.6, 122.9, 120.2, 110.9, 103.3, 98.5, 80.9, 77.5, 75.6, 71.6, 71.3, 66.6, 56.1, 44.5. IR (film): 3054, 2925, 2854, 2822, 2777, 1556, 1256, 980, 746, 700 cm -1. HRMS (ESI) calcd for C 34 H 32 56 FeNO 2 [M+H] + : 542.1777, Found: 542.1783. S30

(R p )-1-(Bezofuran-2-yl)-2-dimethylaminomethyl-3-(diphenylphosphino)ferrocene (4b) Red solid (416.0 mg, 64% yield). Analytical data for 4b: m.p. = 68.9-71.0 o C. [α] D 20 = +111.8 (c = 0.1 Acetone). 1 H NMR (400 MHz, CDCl 3 ) δ 7.641-7.638 (m, 2H), 7.57 (d, J = 7.2 Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.41 (s, 3H), 7.34-7.21 (m, 7H), 7.06 (s, 1H), 5.04 (d, J = 2.0 Hz, 1H), 4.19 (d, J = 2.4 Hz, 1H), 3.98 (d, J = 12.4 Hz, 1H), 3.92-3.91 (m, 1H), 3.89 (s, 5H), 2.05 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 155.2 (d, J = 129.4 Hz), 139.8 (d, J = 8.2 Hz), 138.2 (d, J = 9.0 Hz), 135.3 (d, J = 21.6 Hz), 132.6 (d, J = 18.6 Hz), 129.4 (d, J = 43.1 Hz), 128.1 (d, J = 8.2 Hz), 127.8 (d, J =6.7 Hz), 127.7, 123.1 (d, J = 75.9 Hz), 120.4, 106.9 (d, J = 769 Hz), 88.9 (d, J = 26.7 Hz), 79.6 (d, J = 11.1 Hz), 78.9 (d, J = 4.4 Hz), 72.1 (d, J = 4.5 Hz), 71.3, 70.0, 56.6 (d, J = 12.4 Hz), 44.9. 31 P NMR (161 MHz, CDCl 3 ) δ -25.5. IR (film): 3055, 2925, 2853, 2822, 2776, 1456, 1255, 1174, 746, 699 cm -1. HRMS (ESI) calcd for C 33 H 31 56 FeNOP [M+H] + : 544.1491, Found: 544.1487. (R p )-1-(Bezofuran-2-yl)-2-dimethylaminomethyl-3-(trimethylsilyl)ferrocene (4c) Red oil (340 mg, 66% yield). Analytical data for 4c: [α] 20 D = +304.1 (c = 0.1 Acetone). 1 H NMR (400 MHz, CDCl 3 ) δ 7.62-7.56 (m, 2H), 7.34-7.26 (m, 2H), 6.95 (s, 1H), 4.98 (d, J = 2.4 Hz, 1H), 4.30 (d, J = 2.0 Hz, 1H), 4.13 (s, 5H), 3.77 (AB, J AB = 12.4 Hz, 1H), 3.60 (BA, J BA = 12.4 Hz, 1H), 2.24 (s, 6H), 0.41 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.7, 154.5, 129.6, 123.4, 122.7, 120.3, 110.8, 102.8, 88.4, 78.8, 75.1, 74.7,70.6, 70.5, 57.4, 44.9, 0.7. IR (film): 3092, 3067, 2950, 2815, 2765, 1457, 1255, 1003, 834, 749, 689 cm -1. HRMS (ESI) calcd for C 24 H 56 30 FeNOSi [M+H] + : 432.1441, Found: 432.1443. Note: the lithium step was kept at 0 o C for 5 h. S31