*3.2. Preparation of Starting Materials*

*(+)-(1S,2R)-1-Bromo-N-(tert-butyl)-2-methyl-2-phenylcyclopropane-1-carboxamide* (**20aa**). Typical procedure A. A flame dried 100 mL round-bottom flack, equipped with drying tube and magnetic stir bar, was charged with (1*S*,2*R*)-1-bromo-2-methyl-2-phenylcyclopropane carboxylic acid (**19a**) (1.10 g, 4.33 mmol, 1.00 equiv.), DMF (10 mL), and anhydrous dichloromethane (40 mL). The mixture was treated with oxalyl chloride (563 μL, 6.50 mmol, 1.50 equiv.) at 0 ◦C, stirred for 15 min, warmed to room temperature, and additionally stirred for 2 h. The solvent was removed in vacuum, and the crude acyl chloride was dissolved in dry THF (20 mL), followed by addition of a solution of *tert*-butyl amine (**24a**) (1.35 mL, 12.8 mmol, 2.97 equiv.) in THF (20 mL). The reaction mixture was stirred overnight. After the reaction was complete, the solvent was removed in vacuum, and the residue was partitioned between EtOAc (25 mL) and water (25 mL). The organic phase was separated, and the aqueous layer was extracted with EtOAc (2 × 25 mL). The combined organic phases were dried (MgSO4), filtered, and concentrated. The residual crude oil was purified by column chromatography on silica gel. The titled compound obtained a colorless solid, mp: 83.2–86.0 ◦C, Rƒ 0.55 (hexanes/EtOAc 6:1), [α]D = +14.0◦ (c 0.172, CH2Cl2). Yield 1.03 g (3.32 mmol, 77%). Spectral properties of this material were identical to those reported for the racemic amide [67].

*(+)-(1R,2S)-1-Bromo-N,N,2-trimethyl-2-phenylcyclopropane-1-carboxamide* (**20ab**). Compound was obtained via typical procedure A, employing (1*R*,2*S*)-1-bromo-2-methyl-2-phenylcyclopropane-1-carboxylic acid (**19a**) (510 mg, 2.01 mmol, 1.00 equiv.), oxalyl chloride (260 μL, 3.03 mmol, 1.51 equiv), and 40 wt.% aq solution of dimethyl amine (**24b**) (753 μL, 8.91 mmol, 4.43 equiv.). Chromatographic purification afforded title compound as a colorless solid, mp: 81.7–83.3 ◦C, Rƒ 0.34 (hexanes/EtOAc 10:1), [α]D = +13.3◦ (c 0.098, CH2Cl2). Yield 466 mg (1.66 mmol, 83%). 1H NMR (500 MHz, CDCl3) *δ*<sup>H</sup> 7.43–7.10 (m, 5H), 2.65 (s, 3H), 2.57 (d, <sup>2</sup>*J*H,H = 7.4 Hz, 1H), 2.56 (s, 3H) 1.85 (s, 3H), 1.37 (d, <sup>2</sup>*J*H,H = 7.4 Hz, 1H); 13C NMR (126 MHz, CDCl3) *δ*<sup>C</sup> 166.5, 138.2, 128.1 (+, 2C), 127.1 (+, 2C), 126.3, 42.6,

38.5 (+), 30.8, 27.0 (-), 24.1 (+); FT IR (KBr, cm−1): 2927, 1647, 1558, 1496, 1396, 1272, 1176, 1082, 1058, 1029, 954, 763, 696, 680, 669, 650; HRMS (TOF ES): found 281.0415, calculated for C13H16BrNO (M+) 281.0415 (0.0 ppm).

*(+)-(1S,2R)-1-Bromo-N,N-diethyl-2-methyl-2-phenylcyclopropane-1-carboxamide* (**20ac**). Compound was obtained via typical procedure A, employing (1*S*,2*R*)-1-bromo-2-methyl-2-phenylcyclopropane-1-carboxylic acid (**19a**) (515 mg, 2.02 mmol, 1.00 equiv.), oxalyl chloride (260 μL, 3.03 mmol, 1.50 equiv.), and diethyl amine (**24c**) (823 μL, 7.96 mmol, 3.96 equiv.). Chromatographic purification afforded title compound as a light yellow solid, mp: 74.3–76.2 ◦C, Rƒ 0.34 (hexanes/EtOAc 10:1), [α] 25D = +17.0◦ (c 0.194, CH2Cl2). Yield 537 mg (1.74 mmol, 86%). 1H NMR (500 MHz, CDCl3) *δ*<sup>H</sup> 7.43–7.04 (m, 5H), 3.48 (dq, <sup>2</sup>*J*H,H = 14.2, <sup>3</sup>*J*H,H = 7.1 Hz, 1H), 3.37 (dq, <sup>2</sup>*J*H,H = 14.2, <sup>3</sup>*J*H,H = 7.1 Hz, 1H), 2.71 (dq, <sup>2</sup>*J*H,H = 14.0, <sup>3</sup>*J*H,H = 7.1 Hz, 1H) 2.65 (d, <sup>2</sup>*J*H,H = 7.3 Hz, 1H), 2.58 (dq, <sup>2</sup>*J*H,H = 14.0, <sup>3</sup>*J*H,H = 7.0 Hz, 1H), 1.85 (s, 3H), 1.33 (d, <sup>2</sup>*J*H,H = 7.3 Hz, 1H), 1.0 (t, <sup>3</sup>*J*H,H = 7.1 Hz, 3H) 0.47 (t, <sup>3</sup>*J*H,H = 7.1 Hz, 3H); 13C NMR (126 MHz, CDCl3) *δ*<sup>C</sup> 165.8, 138.1, 128.1 (+), 127.0 (+), 126.7 (+), 42.4, 42.0 (-), 38.3 (-), 31.0, 26.9 (-), 24.3 (+), 12.6 (+), 11.1 (+); FT IR (KBr, cm−1): 2977, 2933, 1643, 1639, 1498, 1456, 1433, 1380, 1282, 1219, 1064, 719, 696, 582; HRMS (TOF ES): found 309.0724, calculated for C15H20BrNO (M+) 309.0728 (1.3 ppm).

*(-)-(1S,2R)-1-Bromo-N-benzyl-1-bromo-2-methyl-2-phenylcyclopropane-1-carboxamide* (**20ad**). Compound was obtained via typical procedure A, employing (1*S*,2*R*)-1-bromo-2-methyl-2-phenylcyclopropane carboxylic acid (**19a**) (255 mg, 1.00 mmol, 1.00 equiv.), oxalyl chloride (130 μL, 1.50 mmol, 1.50 equiv.), and benzyl amine (**24d**) (327 μL, 3.00 mmol, 3.0 equiv). Chromatographic purification afforded a colorless solid, mp: 88.2-91.3 ◦C, Rƒ 0.36 (hexanes/EtOAc 6:1), [α] 25D <sup>=</sup> −115.2◦ (c 0.046, CH2Cl2). Yield 240 mg (0.700 mmol, 70%). Spectral properties of this material were identical to those reported for the racemic amide [67].

*(+)-(1S,2R)-1-Bromo-2-methyl-2-phenylcyclopropyl)(pyrrolidin-1-yl)methanone* (**20ae**). Compound was obtained via typical procedure A, employing (1*S*,2*R*)-1-bromo-2-methyl-2 phenylcyclopropane carboxylic acid (**19a**) (255 mg, 1.00 mmol, 1.00 equiv.), oxalyl chloride (130 μL, 1.50 mmol, 1.50 equiv.) and pyrrolidine (**24e**) (246 μL, 3.00 mmol, 3.00 equiv). Chromatographic purification afforded a colorless oil, Rƒ 0.39 (hexanes/EtOAc, 3:1), [α] 25D = +12.5◦ (c 0.172, CH2Cl2). Yield 289 mg (0.941 mmol, 94%). Spectral properties of this material were identical to those reported for the racemic amide [67].

*(+)-(1R,2S)-1-Bromo-N-(tert-butyl)-2-ethyl-2-phenylcyclopropane-1-carboxamide* (**20ba**). Compound was obtained via typical procedure A, employing (1*R*,2*S*)-1-bromo-2 ethyl-2-phenylcyclopropane carboxylic acid (**19b**) (1.00 g, 3.73 mmol, 1.00 equiv.), oxalyl chloride (711 μL, 5.60 mmol, 1.50 equiv.) and *tert*-butyl amine (**24a**) (1.18 mL, 11.2 mmol, 3.00 equiv.). Chromatographic purification afforded a colorless solid, mp: 63.8–65.7 ◦C, Rƒ 0.52 (hexanes/EtOAc 9:1), [α] 25D = +5.8◦ (c 0.052, CH2Cl2). Yield 1.06 g (3.27 mmol, 88%). Spectral properties of this material were identical to those reported for the racemic amide [67].

*(+)-(1S,2R)-1-Bromo-N-(tert-butyl)-2-methyl-2-(p-tolyl)cyclopropane-1-carboxamide* (**20ca**). Compound was obtained via typical procedure A (1*S*,2*R*)-1-bromo-2-methyl-2-(*p*tolyl)cyclopropane-1-carboxylic acid (**19c**) (240 mg, 0.89 mmol, 1.00 equiv.), oxalyl chloride (116 μL, 1.35 mmol, 1.52 equiv.) and *tert*-butyl amine (**24a**) (280 μL, 2.67 mmol, 3.00 equiv.). Chromatographic purification afforded a colorless solid, mp: 78.4–81.2 ◦C, Rƒ 0.35 (hexanes/EtOAc 20:1), [α] 25D = +14.3◦ (c 0.071, CH2Cl2). Yield 225 mg (0.694 mmol, 78%). Spectral properties of this material were identical to those reported previously [67].

*(-)-(1R,2S)-1-Bromo-N-(tert-butyl)-2-methyl-2-(naphthalen-2-yl)cyclopropane-1 carboxamide* (**20da**). Compound was obtained via typical procedure A, employing (1*R*,2*S*)- 1-bromo-2-methyl-2-naphthalen-2-yl)cyclopropane-1-carboxylic acid (**19d**) (608 mg, 1.99 mmol, 1.00 equiv.), oxalyl chloride (260 μL, 3.00 mmol, 1.51 equiv.), and *tert*-butyl amine (**24a**) (630 μL, 6.00 mmol, 3.02 equiv). Chromatographic purification afforded title compound as a colorless solid, mp: 88.1–89.6 ◦C, Rƒ 0.32 (hexanes/EtOAc 20:1), [α] 25D <sup>=</sup> −41.9◦ (c 0.418, CH2Cl2). Yield 427 mg (1.19 mmol, 60%). 1H NMR (400 MHz, CDCl3)

*<sup>δ</sup>*<sup>H</sup> 7.82–7.68 (m, 3H), 7.65 (d, <sup>3</sup>*J*H,H = 1.2 Hz, 1H), 7.46–7.39 (m, 2H) 7.35 (dd, <sup>3</sup>*J*H,H = 8.5, <sup>4</sup>*J*H,H = 1.8 Hz, 1H), 6.32 (br. s, 1H), 2.69 (d, <sup>2</sup>*J*H,H = 6.3 Hz, 1H), 1.78 (s, 3H), 1.34 (d, <sup>2</sup>*J*H,H = 6.3 Hz, 1H), 1.03 (s, 9H); 13C NMR (126 MHz, CDCl3) *δ*<sup>C</sup> 165.3, 138.2, 133.3, 132,5, 128.0 (+), 127.8 (+), 127.7 (+), 126.8 (+) 126.3 (+), 126.1 (+), 125.7 (+), 51.6, 45.2, 35.1, 28.4 (+, 3C), 28.1 (+), 26.6(-); FT IR (KBr, cm<sup>−</sup>1): 3421, 3053, 2964, 2925, 1678,1599, 1512, 1454, 1392, 1363, 1290, 1221, 1134, 1063, 958, 893, 856, 815, 750; HRMS (TOF ES): found 359.0883, calculated for C19H22BrNO (M+) 359.0885 (0.6 ppm).
