Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals
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1 Supporting Information Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals Zhe Zhou, Zhiwei Ma, Nicole Erin Behnke, Hongyin Gao and László Kürti* Department of Chemistry, Rice University, BioScience Research Collaborative, 6500 Main Street, Rm 380, Houston, TX (USA) Table of Contents Supporting Information... S1 General Remarks... S2 General Procedure for Amination Reactions... S2 1. Preparation of oxaziridine reagents... S2 Synthesis of Di-t-Butyl Oxaziridine 5... S2 2. Preparation of arylmetal reagents... S3 3. Primary Amination... S3 4. Secondary Amination... S3 Analytical data for products... S4 References... S14 Spectral Data... S15 S1
2 General Remarks Solvents were dried by passage through an activated alumina column under argon. All reactions were carried out in flame-dried glassware under an atmosphere of argon with magnetic stirring. All reactions were monitored by thin-layer chromatography (TLC) with E. Merck silica gel 60 F254 pre-coated plates (0.25 mm). Flash chromatography was carried out using a Biotage Isolera One system with 25g KP-Sil cartridges. Proton ( 1 H) and carbon ( 13 C) NMR spectra were recorded on a Bruker DRX-600 spectrometer operating at 600 MHz for proton and 151 MHz for carbon nuclei using CDCl 3 or DMSO-d 6 as solvent, respectively. Chemical shifts are expressed as parts per million (δ, ppm) and are referenced to 7.26 (CDCl 3 ) for 1 H NMR and (CDCl 3 ) for 13 C NMR. Proton signal data uses the following abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad and J = coupling constant. High Resolution Mass Spectrometry was performed on an Agilent 1290/6230 LCMS- TOF under the conditions of electrospray ionization (ESI) in both positive and negative mode. General Procedure for Amination Reactions 1. Preparation of oxaziridine reagents Oxaziridines 3-5 were prepared according to the optimized procedures our group recently published. 1 The detailed procedure for the preparation of oxaziridine 5 is described below. Synthesis of Di-t-Butyl Oxaziridine 5 To a solution of 2,2,4,4-tetramethylpentan-3-imine (5 g, 35 mmol) in 20 ml of CH 2 Cl 2 was added dropwise a solution of m-cpba (7.1 g, 39 mmol, 1.1 equiv) in 80 ml of CH 2 Cl 2 at 0 o C. The reaction mixture was stirred at 0 o C for 3 hours, and then concentrated in vacuo to remove half of the solvent and filtered the m-chlorobenzoic acid by-product from the mixture. Hexanes (50 ml) was added and the solution again concentrated in vacuo until approximately 25% of the original volume remained. This process was repeated once more and finally hexanes (50 ml) was added to the mixture. The precipitated m-chlorobenzoic acid was removed by filtration, and the rest of this by-product washed out of the resulting solution with aqueous sodium hydroxide (1.0 M, 3 x 50 ml). The organic solution was dried (Na 2 SO 4 ) and the solvent was removed in vacuo to give the crude oxaziridine, which can be further purified by column chromatography (Hexanes:EtOAc = 40:1) over silica gel to give di-t-butyl oxaziridine 5 as a colorless oil (4.2 g, 76%). 1 H NMR (600 MHz, CDC1 3 ): δ 3.78 (br s, 1H), 1.13 (s, 9H), 1.09 (s, 9H); 13 C NMR (151 MHz, CDC1 3 ): δ 85.2, 37.5, 28.1, S2
3 2. Preparation of arylmetal reagents Organozinc reagents were either purchased from Rieke Metals, Inc. or, in the case of 21, prepared according to Knochel s procedure. 2 Immediately before using, these reagents were titrated using Iodine following a procedure developed by Knochel et. al. Organolithium reagents were prepared via lithium exchange: 1 mmol corresponding aryl halide was dissolved in 5 ml anhydrous THF and the solution was cooled to -78ºC. To this solution was added a solution of 1.1 mmol n-buli in hexanes at -78ºC and the reaction was stirred for 30 min at -78ºC before used in the next step. Grignard reagents were prepared using one of the following methods: a. Aryl halide and freshly activated Mg turnings was mixed in anhydrous THF. The reaction was activated with small amount of 1,2-dibromoethane and the resulting Grignard reagent was titrated before using. b. Br-Mg exchange using i-prmgcl LiCl as described by Knochel et. al. 3 c. Direct magnesiation of arenes using TMPMgCl LiCl as described by Knochel et. al Primary Amination To a flame-dried flask was added a solution of arylmetal reagent (1 mmol in THF) under argon. The aryl metal solution was cooled to -78ºC and a solution of CuCN 2LiCl (or CuCl 2LiCl) (1 M in THF, 1.1 ml, 1,1 mmol, 1.1 eq.) was added. After 30min at -78ºC, a solution of oxaziridine 5 (1.2 mmol, 1.2 eq.) in 2 ml THF was added to the reaction mixture. After 10 min at -78ºC, the reaction was quenched at -78ºC with the addition of 3 ml sat. aq. NH 4 Cl and 5 ml sat. aq. Na 2 S 2 O 3. After allowing the reaction mixture to reach room temperature, it was diluted with 20 ml EtOAc and transferred to a separatory funnel. The organic layer was separated and the aqueous layer was extracted with EtOAc (2 x 20 ml). The combined organic layer was dried over Na 2 SO 4, filtered and concentrated under reduced pressure. The residue was purified using flash chromatography on a Biotage Isolera system to give the corresponding aniline. Traditional manual flash chromatography gave virtually the same yield. 4. Secondary Amination To a flame-dried flask was added a solution of organozinc reagent (1 mmol in THF) under argon and a solution of CuCN 2LiCl (or CuCl 2LiCl) (1 M in THF, 1.1 ml, 1,1 mmol, 1.1 eq.) was added at room temperature. After 30 min at rt, the reaction mixture was cooled to 0ºC and a solution of hydroxylamine 25 (1.2 mmol, 1.2 eq.) in 2 ml THF was added to the reaction mixture. After 2 h at 0ºC, the reaction was quenched at -78ºC with the addition of 3 ml sat. aq. NH 4 Cl and 5 ml sat. aq. Na 2 S 2 O 3. After allowing the reaction mixture to reach room temperature, it was diluted with 20 ml EtOAc and transferred to a separatory funnel. The organic layer was separated and the aqueous layer was extracted with EtOAc (2 x 20 ml). The combined organic layer was dried over Na 2 SO 4, filtered and concentrated under reduced pressure. The residue was purified using flash chromatography on a Biotage Isolera system to give the corresponding aniline. Traditional manual flash chromatography gave virtually the same yield. S3
4 Analytical data for products 4-fluoronaphthalen-1-amine (6) 1 H NMR (600 MHz, CDCl 3 ) δ 8.08 (d, J = 8.3 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.53 (p, J = 6.8 Hz, 2H), 6.98 (dd, J = 10.3, 8.1 Hz, 1H), 6.66 (dd, J = 8.1, 4.4 Hz, 1H), 3.99 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 153.6, 152.0, 138.3, 138.2, 126.2, 125.9, 124.7, 124.7, 124.3, 124.2, 121.3, 121.2, 109.6, 109.5, 108.8, F (470 MHz, CDCl 3 ) δ Yield: 53%. Purple waxy solid. HRMS (ESI) m/z calcd for [C 10 H 9 FN] + [M+H] + : , found amino-2-fluorobenzonitrile (7) 1 H NMR (600 MHz, CDCl 3 ) δ 6.96 (t, J = 8.7 Hz, 1H), (m, 1H), (m, 1H), 3.83 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 157.3, 155.7, 143.4, 143.3, 121.3, 121.2, 117.6, 117.1, 117.0, 114.5, 101.2, F (470 MHz, CDCl 3 ) δ Yield: 86%. White solid, MP: 97.2 C HRMS (ESI) m/z calcd for [C 7 H 6 FN 2 ] + [M+H] + : , found ,4-dichloroaniline (8) 1 H NMR (600 MHz, CDCl 3 ) δ 7.17 (d, J = 8.6 Hz, 1H), 6.76 (s, 1H), 6.50 (d, J = 8.4 Hz, 1H), 3.71 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 146.1, 132.8, 130.8, 121.2, 116.5, Yield: 65%. Tan solid. MP: 72 C (lit. 5 ) HRMS (ESI) m/z calcd for [C 6 H 6 Cl 2 N] + [M+H] + : , found S4
5 ethyl 3-aminobenzoate (2) 1 H NMR (600 MHz, CDCl 3 ) δ 7.44 (d, J = 7.6 Hz, 1H), 7.37 (s, 1H), 7.21 (t, J = 7.8 Hz, 1H), 6.87 (d, J = 8.1 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 3.69 (s, 2H), 1.38 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 166.9, 146.1, 131.6, 129.4, 120.1, 119.7, 116.1, 77.4, 77.2, 76.9, 61.0, Yield: 90%. Colorless oil. HRMS (ESI) m/z calcd for [C 9 H 12 NO 2 ] + [M+H] + : , found methyl 2-amino-5-chlorobenzoate (9) 1 H NMR (600 MHz, CDCl 3 ) δ 7.82 (d, J = 2.5 Hz, 1H), 7.20 (dd, J = 8.8, 2.6 Hz, 1H), 6.60 (d, J = 8.8 Hz, 1H), 5.73 (s, 2H), 3.87 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 167.7, 149.1, 134.2, 130.5, 120.8, 118.1, 111.6, Yield: 88%. White solid. MP: C (lit. 6 ) HRMS (ESI) m/z calcd for [C 8 H 9 ClNO 2 ] + [M+H] + : , found aminophenyl acetate (10) 1 H NMR (600 MHz, CDCl 3 ) δ 7.12 (t, J = 8.0 Hz, 1H), 6.52 (dd, J = 8.1, 2.2 Hz, 1H), 6.46 (dd, J = 8.1, 2.1 Hz, 1H), 6.39 (t, J = 2.3 Hz, 1H), 3.73 (s, 2H), 2.26 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 169.6, 151.7, 147.8, 130.1, 112.7, 111.3, 108.3, Yield: 62%. Orange waxy solid. HRMS (ESI) m/z calcd for [C 8 H 10 NO 2 ] + [M+H] + : , found S5
6 dibenzo[b,d]furan-2-amine (11) 1 H NMR (600 MHz, CDCl 3 ) δ 7.86 (d, J = 7.6 Hz, 1H), 7.53 (d, J = 8.2 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H), 7.37 (d, J = 8.6 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.22 (d, J = 2.4 Hz, 1H), 6.82 (dd, J = 8.6, 2.5 Hz, 1H), 3.58 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 156.8, 150.4, 142.2, 127.0, 125.0, 124.4, 122.3, 120.6, 115.9, 112.0, 111.7, Yield: 78%. Off-white solid. MP: C HRMS (ESI) m/z calcd for [C 12 H 10 NO] + [M+H] + : , found dibenzo[b,d]thiophen-2-amine (12) 1 H NMR (600 MHz, CDCl 3 ) δ 8.03 (dd, J = 6.1, 2.8 Hz, 1H), 7.82 (dd, J = 6.2, 2.6 Hz, 1H), 7.61 (d, J = 8.4 Hz, 1H), 7.44 (d, J = 2.3 Hz, 1H), 7.41 (td, J = 7.6, 6.9, 3.9 Hz, 2H), 6.87 (dd, J = 8.4, 2.3 Hz, 1H), 3.79 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 144.0, 140.6, 136.8, 135.4, 129.4, 126.6, 124.1, 123.4, 123.0, 121.6, 116.5, Yield: 71%. Off-white solid. MP: C (lit. 7 ) HRMS (ESI) m/z calcd for [C 12 H 10 NS] + [M+H] + : , found methyl-9H-carbazol-3-amine (13) 1 H NMR (600 MHz, CDCl 3 ) δ 8.00 (d, J = 7.8 Hz, 1H), (m, 2H), 7.34 (d, J = 8.2 Hz, 1H), 7.22 (d, J = 8.5 Hz, 1H), 7.17 (t, J = 7.4 Hz, 1H), 6.93 (dd, J = 8.4, 2.3 Hz, 1H), 3.79 (s, 3H), 3.29 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 141.6, 139.1, 135.8, 125.6, 123.6, 122.4, 120.4, 118.2, 115.7, 109.1, 108.5, 106.4, Yield: 61%. Brown solid. MP: 168 C (decomp.) HRMS (ESI) m/z calcd for [C 13 H 13 N 2 ] + [M+H] + : , found S6
7 quinolin-5-amine (14) 1 H NMR (600 MHz, CDCl 3 ) δ 8.88 (d, J = 3.7 Hz, 1H), 8.17 (d, J = 8.4 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), (m, 1H), 7.33 (dd, J = 8.5, 4.2 Hz, 1H), 6.81 (d, J = 7.3 Hz, 1H), 4.22 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 150.4, 149.3, 142.4, 130.1, 129.6, 120.3, 119.7, 118.8, Yield: 67%. Yellow solid. MP: C HRMS (ESI) m/z calcd for [C 9 H 9 N 2 ] + [M+H] + : , found quinolin-3-amine (15) (s, 2H). 1 H NMR (600 MHz, CDCl 3 ) δ 8.50 (d, J = 2.8 Hz, 1H), 7.96 (d, J = 7.9 Hz, 1H), 7.58 (dd, J = 7.6, 2.0 Hz, 1H), (m, 2H), 7.22 (d, J = 2.7 Hz, 1H), C NMR (151 MHz, CDCl 3 ) δ 143.2, 142.9, 139.8, 129.3, 129.2, 127.1, 126.0, 125.7, Yield: 42%. Brown solid. MP: C HRMS (ESI) m/z calcd for [C 9 H 9 N 2 ] + [M+H] + : , found bromoquinolin-2-amine (16) 1 H NMR (600 MHz, CDCl 3 ) δ 8.16 (s, 1H), 7.65 (d, J = 8.3 Hz, 1H), (m, 2H), 7.28 (d, J = 7.6 Hz, 1H), 5.34 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 153.7, 146.7, 139.8, 130.2, 126.8, 126.1, 125.0, 123.4, Yield: 73%. White solid. MP: C HRMS (ESI) m/z calcd for [C 9 H 8 BrN 2 ] + [M+H] + : found S7
8 6-methoxypyridin-2-amine (17) 1 H NMR (600 MHz, CDCl 3 ) δ 7.33 (t, J = 7.8 Hz, 1H), 6.08 (d, J = 7.9 Hz, 1H), 6.05 (d, J = 7.7 Hz, 1H), 4.32 (s, 2H), 3.83 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 163.9, 157.3, 140.4, 99.8, 98.6, Yield: 58%. Orange oil. HRMS (ESI) m/z calcd for [C 6 H 9 N 2 O] + [M+H] + : , found bromopyridin-2-amine (18) 1 H NMR (600 MHz, CDCl 3 ) δ (m, 1H), 6.79 (d, J = 7.5 Hz, 1H), 6.40 (d, J = 8.1 Hz, 1H), 4.66 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 158.7, 140.1, 139.9, 117.1, Yield: 56%. Brown solid. MP: C (lit. 8 ) HRMS (ESI) m/z calcd for [C 5 H 6 BrN 2 ] + [M+H] + : , found bromopyridin-3-amine (19) 1 H NMR (600 MHz, CDCl 3 ) δ 8.02 (s, 1H), 7.96 (d, J = 2.5 Hz, 1H), 7.10 (t, J = 2.1 Hz, 1H), 3.88 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 143.7, 140.4, 135.6, 123.7, Yield: 77%. White solid. MP: C HRMS (ESI) m/z calcd for [C 5 H 6 BrN 2 ] + [M+H] + : , found S8
9 3,5-dibromopyridin-2-amine (20) 1 H NMR (600 MHz, CDCl 3 ) δ 8.05 (d, J = 2.2 Hz, 1H), 7.77 (d, J = 2.1 Hz, 1H), 5.03 (s, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 154.4, 147.4, 142.2, 107.3, Yield: 45%. White solid. MP: C (lit. 9 ) HRMS (ESI) m/z calcd for [C 5 H 5 Br 2 N 2 ] + [M+H] + : , found ,6-dichloropyridazin-4-amine (21) 1 H NMR (600 MHz, DMSO-d 6 ) δ (m, 2H), 6.82 (s, 1H). 13 C NMR (151 MHz, DMSO-d 6 ) δ 154.1, 145.8, 143.3, Yield: 33%. White Solid. MP: C (decomp.) HRMS (ESI) m/z calcd for [C 4 H 4 Cl 2 N 3 ] + [M+H] + : , found ethyl 5-aminothiophene-2-carboxylate (22) 1 H NMR (600 MHz, CDCl 3 ) δ 7.44 (d, J = 4.0 Hz, 1H), 6.08 (d, J = 4.0 Hz, 1H), 4.32 (s, 2H), 4.27 (q, J = 7.1 Hz, 2H), 1.33 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 162.8, 158.8, 134.8, 118.3, 108.0, 60.6, Yield: 83%. Tan oil. HRMS (ESI) m/z calcd for [C 7 H 10 NO 2 S] + [M+H] + : , found S9
10 (8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16- decahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolan]- 2-amine (23) 1 H NMR (600 MHz, CDCl 3 ) δ 6.69 (s, 1H), 6.51 (s, 1H), (m, 4H), 3.82 (s, 3H), 3.65 (s, 2H), (m, 2H), (m, 2H), 2.03 (ddd, J = 14.3, 11.7, 2.6 Hz, 1H), (m, 2H), (m, 2H), 1.63 (td, J = 11.5, 7.1 Hz, 1H), 1.53 (dt, J = 12.5, 3.3 Hz, 1H), (m, 4H), 0.89 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 145.7, 133.8, 132.7, 126.7, 119.6, 112.5, 111.1, 65.3, 64.7, 55.6, 49.5, 46.3, 43.8, 39.3, 34.4, 30.9, 29.4, 27.4, 26.4, 22.5, Yield: 58%. Yellow solid. MP: C HRMS (ESI) m/z calcd for [C 21 H 30 NO 3 ] + [M+H] + : , found ((((R)-2,5,7,8-tetramethyl-2- ((4R,8R)-4,8,12- trimethyltridecyl)chroman-6- yl)oxy)methyl)aniline (24) 1 H NMR (600 MHz, CDCl 3 ) δ 7.20 (t, J = 7.7 Hz, 1H), (m, 2H), 6.67 (d, J = 7.5 Hz, 1H), 4.64 (s, 2H), 3.72 (s, 2H), 2.62 (t, J = 6.8 Hz, 2H), 2.25 (s, 3H), 2.20 (s, 3H), 2.14 (s, 3H), 1.83 (ddt, J = 37.7, 13.3, 6.8 Hz, 2H), (m, 26H), (m, 12H). 13 C NMR (151 MHz, CDCl 3 ) δ 148.3, 148.0, 146.7, 139.4, 129.5, 128.1, 126.1, 123.0, 117.8, 117.7, 114.6, 114.3, 74.9, 74.8, 40.2, 39.5, 37.6, 37.6, 37.6, 37.4, 32.9, 32.8, 31.5, 28.1, 24.9, 24.6, 24.0, 22.9, 22.8, 21.2, 20.8, 19.9, 19.8, 13.0, 12.1, Yield: 55%. Light yellow oil. HRMS (ESI) m/z calcd for [C 36 H 58 NO 2 ] + [M+H] + : , found S10
11 N-cyclohexyl-2-methoxyaniline (26) 1 H NMR (600 MHz, CDCl 3 ) δ 6.89 (t, J = 7.4 Hz, 1H), 6.80 (d, J = 7.5 Hz, 1H), 6.67 (t, J = 7.1 Hz, 2H), 4.04 (s, 1H), 3.87 (s, 3H), 3.30 (tt, J = 10.1, 3.8 Hz, 1H), 2.12 (dd, J = 12.9, 4.0 Hz, 2H), 1.82 (dt, J = 13.4, 4.0 Hz, 2H), 1.70 (dt, J = 12.9, 3.9 Hz, 1H), 1.43 (qt, J = 12.0, 3.5 Hz, 2H), (m, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 146.8, 137.3, 121.3, 115.9, 110.3, 109.6, 55.4, 51.4, 33.5, 26.1, O N H Yield: 71%. Light yellow oil. HRMS (ESI) m/z calcd for [C 13 H 20 NO] + [M+H] + : , found F CN N H 1.31 (m, 2H), (m, 3H). 5-(cyclohexylamino)-2-fluorobenzonitrile (27) 1 H NMR (600 MHz, CDCl 3 ) δ 6.96 (t, J = 8.8 Hz, 1H), 6.71 (dd, J = 9.0, 3.9 Hz, 1H), (m, 1H), 3.64 (s, 1H), (m, 1H), (m, 2H), 1.77 (dt, J = 13.6, 4.1 Hz, 2H), 1.66 (dt, J = 13.0, 4.0 Hz, 1H), C NMR (151 MHz, CDCl 3 ) δ (d, J = Hz), (d, J = 1.8 Hz), 119.4, (dd, J = 20.7, 4.1 Hz), (d, J = 13.3 Hz), 101.3, 52.2, 33.2, 25.9, F (470 MHz, CDCl 3 ) δ Yield: 57%. White solid. MP: C HRMS (ESI) m/z calcd for [C 13 H 16 FN 2 ] + [M+H] + : , found S11
12 Cl 3,4-dichloro-N-cyclohexylaniline (28) Cl N H 1 H NMR (600 MHz, CDCl 3 ) δ 7.14 (d, J = 8.7 Hz, 1H), 6.63 (d, J = 2.7 Hz, 1H), 6.39 (dd, J = 8.8, 2.8 Hz, 1H), 3.48 (s, 1H), 3.18 (ddd, J = 14.0, 10.2, 3.8 Hz, 1H), (m, 2H), 1.76 (dt, J = 13.6, 4.0 Hz, 2H), 1.66 (dt, J = 12.9, 4.0 Hz, 1H), (m, 2H), (m, 1H), (m, 2H). 13 C NMR (151 MHz, CDCl 3 ) δ 147.0, 132.9, 130.7, 119.1, 114.0, 112.9, 51.9, 33.3, 25.9, Yield: 76%. Brown solid. MP: C HRMS (ESI) m/z calcd for [C 12 H 16 Cl 2 N] + [M+H] + : , found methyl 5-chloro-2-(cyclohexylamino)benzoate (29) NH Cl CO 2 Me 1.28 (m, 3H). 1 H NMR (600 MHz, CDCl 3 ) δ 7.85 (d, J = 2.7 Hz, 1H), 7.74 (d, J = 7.6 Hz, 1H), 7.24 (dd, J = 9.1, 2.7 Hz, 1H), 6.63 (d, J = 9.1 Hz, 1H), 3.85 (s, 3H), 3.36 (qd, J = 9.2, 7.6, 3.9 Hz, 1H), (m, 2H), 1.76 (dt, J = 13.4, 4.3 Hz, 2H), 1.62 (dt, J = 13.2, 4.1 Hz, 1H), 1.39 (dtt, J = 13.2, 10.4, 3.2 Hz, 3H), C NMR (151 MHz, CDCl 3 ) δ 168.3, 149.1, 134.5, 131.2, 131.1, 118.5, 113.3, 113.2, 110.4, 51.8, 51.7, 50.8, 32.9, 26.0, 24.7, Yield: 61%. Yellow oil. HRMS (ESI) m/z calcd for [C 14 H 19 ClNO 2 ] + [M+H] + : , found CO 2 Et ethyl 3-(cyclohexylamino)benzoate (30) 1 H NMR (600 MHz, CDCl 3 ) δ 7.32 (d, J = 7.6 Hz, 1H), 7.25 (t, J = 2.1 Hz, 1H), N 7.19 (t, J = 7.8 Hz, 1H), 6.74 (dd, J = 8.1, 2.4 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), H 3.65 (s, 1H), 3.31 (td, J = 9.8, 4.8 Hz, 1H), 2.05 (dd, J = 13.0, 4.0 Hz, 2H), 1.76 (dt, J = 13.6, 4.0 Hz, 2H), 1.66 (dt, J = 12.9, 3.9 Hz, 1H), (m, 5H), (m, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 167.3, 147.5, 131.5, 129.3, 118.0, 117.5, 113.9, 60.9, 51.7, 33.5, 26.0, 25.1, Yield: 65%. Brown oil. S12
13 HRMS (ESI) m/z calcd for [C 15 H 22 NO 2 ] + [M+H] + : , found EtO 2 C S N H ethyl 5-(cyclohexylamino)thiophene-2-carboxylate (31) 1 H NMR (600 MHz, CDCl 3 ) δ 7.48 (d, J = 4.2 Hz, 1H), 5.90 (d, J = 4.2 Hz, 1H), 4.34 (d, J = 7.9 Hz, 1H), 4.27 (q, J = 7.1 Hz, 2H), 3.17 (tdt, J = 10.6, 7.7, 3.8 Hz, 1H), (m, 2H), 1.76 (dt, J = 13.5, 4.1 Hz, 2H), 1.65 (dt, J = 13.0, 4.0 Hz, 1H), (m, 5H), 1.22 (dddt, J = 18.5, 11.4, 6.6, 3.4 Hz, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 163.0, 161.4, 135.2, 114.9, 103.7, 60.4, 56.3, 33.1, 25.7, 24.9, Yield: 49%. Brown oil. HRMS (ESI) m/z calcd for [C 13 H 20 NO 2 S] + [M+H] + : , found (R)-2-methoxy-N-(1-phenylethyl)aniline (32) 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), 7.33 (t, J = 7.6 Hz, 2H), (m, 1H), 6.79 (dd, J = 7.9, 1.4 Hz, 1H), 6.72 (td, J = 7.7, 1.4 Hz, 1H), 6.63 (td, J = 7.7, 1.6 Hz, 1H), 6.37 (dd, J = 7.9, 1.5 Hz, 1H), 4.66 (s, 1H), 4.50 (q, J = 6.7 Hz, 1H), 3.91 (s, 3H), 1.58 (d, J = 6.8 Hz, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 146.7, 145.6, 137.3, 128.7, 126.9, 126.0, 121.3, 116.4, 111.1, 109.4, 55.6, 53.4, Yield: 83%. Brown solid. MP: C HRMS (ESI) m/z calcd for [C 15 H 18 NO] + [M+H] + : , found (R)-ethyl 3-((1-phenylethyl)amino)benzoate (33) 1 H NMR (600 MHz, CDCl 3 ) δ 7.38 (d, J = 7.3 Hz, 2H), (m, 3H), 7.30 (t, J = 2.1 Hz, 1H), 7.25 (t, J = 7.3 Hz, 1H), 7.14 (t, J = 7.9 Hz, 1H), 6.66 (dd, J = 8.1, 2.4 Hz, 1H), 4.55 (q, J = 6.8 Hz, 1H), 4.34 (q, J = 7.1 Hz, 2H), 4.25 (s, 1H), 1.55 (d, J = 6.7 Hz, 3H), 1.37 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 167.0, 147.3, 144.8, 131.3, 129.1, 128.8, 127.1, 125.9, 118.4, 117.3, 114.5, 60.8, 53.5, 24.9, Yield: 88%. Light yellow solid. MP: C HRMS (ESI) m/z calcd for [C 17 H 20 NO 2 ] + [M+H] + : , found S13
14 N-cyclohexyl-3-((((R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6- yl)oxy)methyl)aniline (34) 1 H NMR (600 MHz, CDCl 3 ) δ 7.19 (t, J = 7.9 Hz, 1H), 6.78 (d, J = 6.7 Hz, 2H), 6.58 (d, J = 8.0 Hz, 1H), 4.63 (s, 2H), 3.30 (td, J = 9.9, 4.9 Hz, 1H), 2.60 (t, J = 6.8 Hz, 2H), 2.23 (s, 3H), 2.18 (s, 3H), 2.12 (s, 3H), (m, 2H), 1.81 (ddt, J = 37.4, 13.0, 6.9 Hz, 4H), 1.67 (dt, J = 12.9, 4.0 Hz, 1H), 1.56 (ddt, J = 19.7, 13.3, 5.9 Hz, 3H), (m, 27H), 0.88 (dd, J = 12.7, 6.7 Hz, 12H). 13 C NMR (151 MHz, CDCl 3 ) δ 148.3, 148.0, 147.6, 139.3, 129.5, 128.1, 126.1, 123.0, 117.7, 116.3, 112.6, 112.5, 75.1, 74.9, 51.9, 40.2, 39.5, 37.6, 37.6, 37.6, 37.4, 33.6, 32.9, 32.9, 31.5, 28.1, 26.1, 25.1, 25.0, 24.6, 24.0, 22.9, 22.8, 21.2, 20.8, 19.9, 19.9, 19.8, 13.0, 12.2, Yield: 60%. Brown oil. HRMS (ESI) m/z calcd for [C 42 H 68 NO 2 ] + [M+H] + : , found References 1. Gao, H.; Zhou, Z.; Kwon, D.-H.; Coombs, J.; Jones, S.; Behnke, N. E.; Ess, D. H.; Kürti, L. Nat. Chem. 2016, advance online publication. 2. Wunderlich, S. H.; Knochel, P. Angew. Chem. Int. Ed. 2007, 46, Krasovskiy, A.; Knochel, P. Angew. Chem. Int. Ed. 2004, 43, Krasovskiy, A.; Krasovskaya, V.; Knochel, P. Angew. Chem. Int. Ed. 2006, 45, Rangappa, K.; Chandrappa, S.; Vinaya, K.; Ramakrishnappa, T. Synlett 2010, 2010, Leiby, R. W. J. Org. Chem 1985, 50, Kudo, H.; Castle, R. N.; Lee, M. L. J. Heterocyclic Chem. 1985, 22, Zhang, E.-X.; Wang, D.-X.; Huang, Z.-T.; Wang, M.-X. J. Org. Chem. 2009, 74, Paudler, W. W.; Jovanovic, M. V. J. Org. Chem. 1983, 48, S14
15 Spectral Data S15
16 NH 2 F Compound 6 1 H NMR (CDCl 3, 600 MHz) S16
17 NH 2 F Compound 6 13 C NMR (CDCl 3, 151 MHz) S17
18 NH 2 F Compound 6 19 F NMR (CDCl 3, 470 MHz) S18
19 NH 2 F Compound 6 19 F NMR (CDCl 3, 470 MHz) S19
20 F CN NH 2 Compound 7 1 H NMR (CDCl 3, 600 MHz) S20
21 F CN NH 2 Compound 7 13 C NMR (CDCl 3, 151 MHz) S21
22 F CN NH 2 Compound 7 19 F NMR (CDCl 3, 470 MHz) S22
23 F CN NH 2 Compound 7 19 F NMR (CDCl 3, 470 MHz) S23
24 NH 2 Cl Cl Compound 8 1 H NMR (CDCl 3, 600 MHz) S24
25 NH 2 Cl Cl Compound 8 13 C NMR (CDCl 3, 151 MHz) S25
26 O O NH 2 Compound 2 1 H NMR (CDCl 3, 600 MHz) S26
27 O O NH 2 Compound 2 13 C NMR (CDCl 3, 151 MHz) S27
28 O O NH 2 Cl Compound 9 1 H NMR (CDCl 3, 600 MHz) S28
29 O O NH 2 Cl Compound 9 13 C NMR (CDCl 3, 151 MHz) S29
30 O O NH 2 Compound 10 1 H NMR (CDCl 3, 600 MHz) S30
31 O O NH 2 Compound C NMR (CDCl 3, 151 MHz) S31
32 NH 2 O Compound 11 1 H NMR (CDCl 3, 600 MHz) S32
33 NH 2 O Compound C NMR (CDCl 3, 151 MHz) S33
34 NH 2 S Compound 12 1 H NMR (CDCl 3, 600 MHz) S34
35 NH 2 S Compound C NMR (CDCl 3, 151 MHz) S35
36 NH 2 N Compound 13 1 H NMR (CDCl 3, 600 MHz) S36
37 NH 2 N Compound C NMR (CDCl 3, 151 MHz) S37
38 NH 2 N Compound 14 1 H NMR (CDCl 3, 600 MHz) S38
39 NH 2 N Compound C NMR (CDCl 3, 151 MHz) S39
40 NH 2 N Compound 15 1 H NMR (CDCl 3, 600 MHz) S40
41 NH 2 N Compound C NMR (CDCl 3, 151 MHz) S41
42 Br N NH 2 Compound 16 1 H NMR (CDCl 3, 600 MHz) S42
43 Br N NH 2 Compound C NMR (CDCl 3, 151 MHz) S43
44 N O NH 2 Compound 17 1 H NMR (CDCl 3, 600 MHz) S44
45 N O NH 2 Compound C NMR (CDCl 3, 151 MHz) S45
46 Br N NH 2 Compound 18 1 H NMR (CDCl 3, 600 MHz) S46
47 Br N NH 2 Compound C NMR (CDCl 3, 151 MHz) S47
48 Br NH 2 N Compound 19 1 H NMR (CDCl 3, 600 MHz) S48
49 Br NH 2 N Compound C NMR (CDCl 3, 151 MHz) S49
50 Br Br N NH 2 Compound 20 1 H NMR (CDCl 3, 600 MHz) S50
51 Br Br N NH 2 Compound C NMR (CDCl 3, 151 MHz) S51
52 H 2 N Cl N N Cl Compound 21 1 H NMR (DMSO-d 6, 600 MHz) S52
53 H 2 N Cl N N Cl Compound C NMR (DMSO-d 6, 151 MHz) S53
54 NH 2 S O O Compound 22 1 H NMR (CDCl 3, 600 MHz) S54
55 NH 2 S O O Compound C NMR (CDCl 3, 151 MHz) S55
56 H 2 N O H H Me O H O Compound 23 1 H NMR (CDCl 3, 600 MHz) S56
57 H 2 N O H H Me O H O Compound C NMR (CDCl 3, 151 MHz) S57
58 NH 2 O H 3 C CH 3 O CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 Compound 24 1 H NMR (CDCl 3, 600 MHz) S58
59 NH 2 O H 3 C CH 3 CH 3 O CH 3 CH 3 CH 3 CH 3 CH 3 Compound C NMR (CDCl 3, 151 MHz) S59
60 O N H Compound 26 1 H NMR (CDCl 3, 600 MHz) S60
61 O N H Compound C NMR (CDCl 3, 151 MHz) S61
62 F CN N H Compound 27 1 H NMR (CDCl 3, 600 MHz) S62
63 F CN N H Compound C NMR (CDCl 3, 151 MHz) S63
64 F CN N H Compound F NMR (CDCl 3, 470 MHz) S64
65 Cl Cl N H Compound 28 1 H NMR (CDCl 3, 600 MHz) S65
66 Cl Cl N H Compound C NMR (CDCl 3, 151 MHz) S66
67 NH Cl CO 2 Me Compound 29 1 H NMR (CDCl 3, 600 MHz) S67
68 NH Cl CO 2 Me Compound C NMR (CDCl 3, 151 MHz) S68
69 CO 2 Et N H Compound 30 1 H NMR (CDCl 3, 600 MHz) S69
70 CO 2 Et N H Compound C NMR (CDCl 3, 151 MHz) S70
71 EtO 2 C S N H Compound 31 1 H NMR (CDCl 3, 600 MHz) S71
72 EtO 2 C S N H Compound C NMR (CDCl 3, 151 MHz) S72
73 N H O Compound 32 1 H NMR (CDCl 3, 600 MHz) S73
74 N H O Compound C NMR (CDCl 3, 151 MHz) S74
75 N H O O Compound 33 1 H NMR (CDCl 3, 600 MHz) S75
76 N H O O Compound C NMR (CDCl 3, 151 MHz) S76
77 N H O Me Me Me O Me Me Me Me Me Compound 34 1 H NMR (CDCl 3, 600 MHz) S77
78 N H O Me Me Me O Me Me Me Me Me Compound C NMR (CDCl 3, 151 MHz) S78
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