實驗部分 - 有機催化連鎖外消旋硝基丙烯醇動力學分割之探討

3-1 分析儀器及基本實驗操作

1. 核磁共振儀（NMR）：以 Bruker Avance 型（400 MHz）和 Bruker Avance 型

（500 MHz）核磁共振光譜儀當做測定的儀器。待測樣品係以氘化氯仿

（CDCl3）作為溶劑，¹H-NMR 之化學位移（，chemical shift）以 ppm 當做光譜單位，並使用四甲基矽烷（tetramethylsilane，TMS）作為內標準，定義 TMS 之化學位移為 0 ppm。分裂形式（splitting pattern）定義：s，單重峰

（singlet）；d，雙重峰（doublet）；t，三重峰（triplet）；q，四重峰（quartet）；

m，多重峰（multiplet）。偶合常數（coupling constant）以 J 表示，單位是 Hz。根據所得光譜數據，紀錄依序為：化學位移（分裂形式，偶合常數，

氫數）。¹³C-NMR 光譜亦透過同樣儀器操作，化學位移以氘化氯仿中間線當作內標準，定義化學位移為 77.0 ppm。

2. 高解析質譜儀（High Resolution Mass Spectroscopy，HRMS）：使用 Waters Premier 型與 JEOL JMS-700 型高解析質譜儀做為測定儀器。係委託中央研究院化學研究所質譜服務中心代為測定（EI 和 ESI）。

3. X 光單晶繞射：係以 Bruker Enraf-Nonius Kappa CCD 或 Bruker Kappa APEX II 儀器作為測定儀器。委託國科會國立臺灣師範大學貴重儀器使用中心代為測定。

4. 分析用薄層色層分析片（Thin Layer Chromatography，TLC）：使用 Silica gel 60 F254 Merck 之玻璃 TLC 薄片，經展開槽展開，並以紫外燈（254 nm）照射或是顯色劑檢視之。

5. 管柱色層分析（Column Chromatography）：使用 Merck Silica gel F60，230-400 mesh ATSM 用作充填物，經加壓快速層析（flash column chromatography），依 Still 的操作方式來分離。沖提液（eluent）若為兩種溶劑系統，則以溶劑體積的比值來配置，記錄方式為兩種溶劑的體積比值。

6. 所有的反應物與溶劑均為試藥等級或分析級，若需純化或乾燥再處理，純化

方式按照 D. D. Perrin；W. L. F. Armarego 及 D. R. Perrin 所著作的 Purifacation of Laboratory Chemicals 的方式進行處理。二氯甲烷、四氫呋喃、乙腈、甲

苯與乙醚均經溶劑純化系統乾燥和純化（active alumina column）。

7. 低溫反應控制裝置：使用 AZO FR140 低溫控制裝置和 UR-8500 型超低溫反應器，並使用工業級異丙醇（IPA）或丙酮為冷劑。

8. 高效能液相層析儀（High Performance Liquid Chromatography，HPLC）：使用 JASCO PU-2089 型高壓幫浦作為動力來源，結合 JASCO UV-2075 型紫外光/可見光檢測器進行樣品分析。

9. 減壓濃縮係使用 Buchi Rotavapor R-114 型、R-200 型及 R-II 型旋轉濃縮機，

並連接空氣式或水流式的抽氣幫浦。

10. 旋光儀：使用 JASCO P2000 型 Digital polarimeter 自動旋光光度計

11. 紅外線光譜儀（IR Spectroscopy）：使用 Perkin Elmer Spectrum 500 型紅外線 光譜儀為測定儀器。

3-2 不對稱連鎖 Michael/縮醛化反應之實驗步驟

The reaction was carried out by taking aldehydes 128（0.2 mmol）, nitro allylic alcohols 129 （ 0.2 mmol ） in presence of 10 mol% ,-L-diphenylprolinol trimethylsilyl ether 46 and benzoic acid（10 mol%）in the DCE（0.4 mL）at 0 ^oC.

Stirring was continued until the consumption closed to 50% of nitro allylic alcohols 129 by using CH₂Br₂ or CHPh₃ as an internal standard and determined by crude

1H-NMR. A residual of crude was purified by flash column chromatography and following gradient elution （ 15% to 20% EtOAc in Hexanes ） to give the corresponding tetrahydropyrans 125 and recovery (S)-129.

3-3 光譜數據 Compound 125a

92% ee, []^25.5D = -54.7 (c = 1.0 in CHCl3); White sticky solid; Rf

= 0.21 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3):

7.38-7.28 (m, 3H), 7.19-7.17 (m, 2H), 5.35 (dd, J = 7.6, 4.4 Hz, 1H), 5.16 (dd, J = 10.2, 5.8 Hz, 1H), 5.05 (d, J = 5.8 Hz, 1H), 4.23 (qd, J = 7.1, 3.5 Hz, 2H), 3.57 (d, 4.4 Hz, 1H), 3.17 (dd, J = 12.4, 10.2 Hz, 1H), 1.93 (ddq, J = 12.4, 7.6, 6.6 Hz, 1H), 1.25 (t, J = 7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 168.0, 137.6, 129.1, 128.1, 128.0, 98.2, 89.8, 69.3, 62.3, 48.2, 39.3, 15.5, 13.8 ppm; FTIR (cm^-1): 3451, 3064, 3029, 2971, 2932, 2356, 2343, 1809, 1757, 1746, 1555, 1496, 1456, 1373, 1261, 1127, 1025, 757, 702, 667, 586;

HRMS (ESI) m/z calcd. for C15H19NO6Na [M+Na]⁺ 332.1110, found 332.1101.;

HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 21.3 min, t_R (major) = 48.6 (min).

Recovery 129f

For recovery alcohol (129f): Spectroscopic data are in agreement with racemic substrate 129f. Isolated yield: 40%. []^25.5D = +62.7 (c = 1.0 in CHCl3). The enantiomeric excess (92% ee) was determined by HPLC with OD-H column, and following the condition: 2-propanol/n-hexane = 5/95, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 26.6 min, t_R (major) = 30.5 (min).

Compound 125b

85% ee, []^25.5D = -17.3 (c = 1.0 in CHCl3); Colorless viscous solid; Rf = 0.20 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 8.25 (d, J = 8.7 Hz, 2H), 7.43 (J = 8.7 Hz, 2H), 5.3 (d, J = 7.5 Hz, 1H), 5.20 (dd, J = 12.2, 5.8 Hz, 1H), 5.11 (d, 5.8 Hz, 1H), 4.29-4.20 (m, 2H), 3.33 (dd, J = 12.2, 10.4 Hz, 1H), 2.00 (ddq, J = 10.4, 7.5, 6.6 Hz, 1H), 1.25 (t, 7.5 Hz, 3H), 0.86 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) :

167.7, 147.7, 145.2, 129.1, 124.3, 97.7, 88.5, 69.3, 62.5, 47.9, 39.3, 15.3, 13.8 ppm;

FTIR (cm^-1): 3451, 2985, 2936, 1748, 1601, 1557, 1522, 1459, 1349, 1224, 1110,

1027, 852, 753; HRMS (ESI) m/z calcd. for C₁₅H₁₈N₂O₈Na [M+Na]⁺ 377.0961, found 377.0956; HPLC conditions: IB column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 24.4 min, tR (major) = 29.7 (min).

Recovery 129a

For recovery alcohol (129a): Spectroscopic data are in agreement with racemic substrate 129a. Isolated yield: 30%.

[]^25.5D = +91.9 (c = 1.0 in CHCl₃). The enantiomeric excess (88% ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 38.5 min, t_R (major) = 64.7 (min).

Compound 125c

96% ee, []^25.5D = -65.0 (c = 1.0 in CHCl₃); Colorless viscous solid; R_f = 0.18 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.17 (dd, J = 8.6, 5.2 Hz, 2H), 7.06 (t, J = 8.6 Hz, 2H), 5.34 (d, J = 7.6 Hz, 1H), 5.12 (dd, J = 10.2, 5.8 Hz, 1H), 5.05 (d, 5.8 Hz, 1H), 4.23 (qd, J = 7.1, 4.4 Hz, 2H), 3.17 (dd, J = 12.4, 10.2 Hz, 1H), 1.91 (ddq, J = 12.4, 7.6, 6.6 Hz, 1H), 1.24 (t, 7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl₃) : 167.8, 129.6, 129.5, 116.2, 116.0, 98.0, 89.6, 69.4, 62.3, 47.4, 39.5, 15.4, 13.8ppm; FTIR (cm^-1):

3446, 2980, 2932, 1757, 1748, 1605, 1555, 1511, 1459, 1373, 1226, 1161, 1128, 1064, 1025, 974, 908, 834, 733; HRMS (ESI) m/z calcd. for C₁₅H₁₈NO₆F [M+Na]⁺ 350.1016, found 350.1020; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 20.8 min, tR

(major) = 57.6 (min).

Recovery 129b

For recovery alcohol (129b): Spectroscopic data are in agreement with racemic substrate 129b. Isolated yield: 37%.

[]^25.5D = +30.6 (c = 1.0 in CHCl3). The enantiomeric excess (89%

ee) was determined by HPLC with AD-H column , and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 16.8 min, tR (major) = 33.8 (min).

Compound 125d

91% ee, []^25.5D = -40.8 (c = 1.0 in CHCl₃); Colorless liquid;

R_f = 0.19 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.34 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 5.33 (d, J = 7.5 Hz, 1H), 5.12 (dd, J = 10.2, 5.8 Hz, 1H), 5.05 (d, J = 5.8 Hz, 1H), 4.23 (qd, J = 7.1, 3.8 Hz, 2H), 3.90 (s, 1H), 3.16 (dd, J = 12.4, 10.2 Hz, 1H), 1.90 (ddq, J = 12.4, 7.5, 6.6 Hz, 1H), 1.25 (t, 7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm;

13C NMR (100 MHz, CDCl₃) : 167.7, 136.1, 134.0, 129.3, 129.3, 97.9, 89.2, 69.5, 62.3, 47.5, 39.4, 15.3, 13.8 ppm; FTIR (cm^-1): 3451, 2958, 2927, 2862, 1722, 1557, 1492, 1460, 1375, 1272, 1121, 1093, 1073, 1018; HRMS (ESI) m/z calcd. for C₁₅H₁₈ClNO₆Na [M+Na]⁺ 366.0720, found 366.0723; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: t_R (minor) = 21.9 min, t_R (major) = 70.6 (min).

Recovery 129c

For recovery alcohol (129c): Spectroscopic data are in agreement with racemic substrate 129c. Isolated yield: 33%.

[]^25.5D = +47.6 (c = 1.0 in CHCl₃). The enantiomeric excess (94%

ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 16.4 min, t_R (major) = 31.0 (min).

Compound 125e

93% ee, []^25.5D = -65.3 (c = 1.0 in CHCl3); Colorless sticky solid; Rf = 0.20 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3):  7.50 (d, J = 8.4 Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H), 5.34 (d, J = 7.5 Hz, 1H), 5.10 (dd, J = 10.2, 5.8 Hz, 1H), 5.04 (d, J = 5.8 Hz, 1H), 4.23 (dd, J = 7.1, 3.1 Hz, 2H), 3.69 (m, 1H), 3.16 (dd, J = 12.4, 10.2 Hz, 1H), 1.9 (ddq, 12.4, 7.5, 6.6 Hz, 1H), 1.25 (t, J = 7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm;

13C NMR (100 MHz, CDCl3) : 167.7, 136.6, 132.3, 129.6, 122.1, 97.8, 891, 69.6, 62.3, 47.5, 39.4, 15.3, 13.8 ppm; FTIR (cm^-1): 3446, 2980, 2927, 2853, 1746, 1555,

1489, 1456, 1375, 1224, 1125, 1068, 976, 854, 823, 755; HRMS (ESI) m/z calcd. for C10H17BrNO6Na [M+Na]⁺ 410.0214, found 410.0221.; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 22.5 min, tR (major) = 73.4 (min).

Recovery 129d

For recovery alcohol (129d): Spectroscopic data are in agreement with racemic substrate 129d. Isolated yield: 33%.

[]^25.5D = +49.2 (c = 1.0 in CHCl3). The enantiomeric excess (96%

ee) was determined by HPLC with OD-H column, and following the condition:

2-propanol/n-hexane = 5/95, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 19.9 min, tR (major) = 29.5 (min). Crystal data for 129d at 200 (2) K:

C12H12BrNO5, M 330.14, Monoclinic, P 21, a = 11.2767 (7) Å , b = 5.3947 (3) Å , c = 11.4249 (8) Å , V = 660.83 (7) Å³, Z = 2, Dx = 1.659 Mg/m³,  = 3.126 mm^-1, 4601 reflections, 172 parameters, R = 0.0222, Rw = 0.0435, flack parameter = 0.009 (6) for all data.

Compound 125f

91% ee, []^25.5D = -70.0 (c = 1.0 in CHCl3); Viscous liquid;

Rf = 0.25 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3): 7.35 (s, 2H), 5.31 (d, J = 7.6 Hz, 1H), 5.07 (dd, J = 9.8, 5.8 Hz, 1H), 5.03 (d, J = 5.8 Hz, 1H), 4.24 (qd, J

= 7.1, 1.8 Hz), 3.89 (s, 3H), 3.33 (s, 1H), 3.14 (dd, J = 12.4, 9.8 Hz, 1H), 1.84 (ddq, J

= 12.4, 7.6, 6.6 Hz, 1H), 1.27 (t, J = 7.1 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 167.7, 153.9, 136.5, 132.1, 118.8, 97.7, 88.6, 69.4, 62.4, 60.7, 46.9, 39.4, 15.4, 13.8 ppm; FTIR (cm^-1): 3442, 2980, 2932, 1748, 1470, 1424, 1375, 1259, 1224, 1123, 1068, 1027, 987; HRMS (ESI) m/z calcd. for C16H19Br2NO7Na [M+Na]⁺ 517.9426, found 517.9423; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 14.5 min, tR (major) = 30.2 (min).

Compound 125g

94% ee, []^25.5D = -81.5 (c = 1.0 in CHCl3); Colorless sticky liquid; Rf = 0.23 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3): 7.16 (d, 8.1 Hz, 2H), 7.06 (d, J = 8.1 Hz, 2H), 5.33 (d, J =7.5 Hz, 1H), 5.14 (dd, J = 10.2, 5.8 Hz, 1H), 5.04 (d, J = 5.8 Hz, 1H), 4.22 (qd, J = 7.1, 4.4 Hz, 2H), 3.12 (dd, J = 12.4, 10.2 Hz, 1H), 2.34 (s, 3H), 2.1 (ddq, J = 12.4, 7.5, 6.6 Hz, 1H), 1.24 (t, J =7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 167.9, 137.7, 134.5, 129.8, 129.6, 127.8, 127.5, 98.1, 89.8, 69.4, 62.2, 47.8, 39.3, 21.1, 15.4, 13.8 ppm; FTIR (cm^-1): 3455, 2976, 2927, 1750, 1555, 1516, 1456, 1373, 1226, 1128, 1064, 1027; HRMS (ESI) m/z calcd. for C16H21NO6Na [M+Na]⁺ 346.1267, found 346.1271; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR

(minor) = 16.3 min, tR (major) = 37.8 (min).

Recovery 129g

For recovery alcohol (129g): Spectroscopic data are in agreement with racemic substrate 129g. Isolated yield: 34%.

[]^25.5D = +16.8 (c = 1.0 in CHCl3).The enantiomeric excess

(94% ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 12.7 min, tR (major) = 33.1 (min).

Compound 125h

97% ee, []^25.5D = -66.2 (c = 1.0 in CHCl₃); Colorless liquid; R_f = 0.18 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.10 (d, J = 8.7 Hz, 2H), 6.88 (d, J

= 8.7, 2H), 5.34 (d, J =7.6 Hz, 1H), 5.12 (dd, J = 10.2, 5.8 Hz, 1H), 5.03 (d, J = 5.8 Hz, 1H), 4.27-4.18 (m, 2H), 3.80 (s, 3H), 3.12 (dd, J = 12.8, 10.2 Hz, 1H), 1.89 (ddq, J = 12.8, 7.6, 6.6 Hz, 1H), 1.24 (t, 7.1 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl₃) : 167.9, 159.3, 129.4, 129.0, 114.5, 98.1, 89.8, 69.5, 62.2, 55.2, 47.4, 39.5, 15.4, 13.8 ppm; HRMS (ESI) m/z calcd. for C₁₆H₂₁NO₇Na [M+Na]⁺ 362.1216, found 362.1217； FTIR (cm^-1): 3451, 2976, 2932, 1750, 1553, 1516, 1463, 1373, 1250, 1178, 1125, 1027, 832; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10-90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR

(minor) = 27.8 min, t_R (major) = 59.9 (min).

Recovery 129h

For recovery alcohol (129h): Spectroscopic data are in agreement with racemic substrate 129h. Isolated yield: 35%.

[]^25.5D = -48.8 (c = 1.0 in CHCl₃). The enantiomeric excess (90% ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 22.5 min, t_R (major) = 57.2 (min).

Compound 125i

97% ee, []^25.5D = -77.1 (c = 1.0 in CHCl3); White solid; Rf

= 0.20 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.29-7.25 (m, 1H), 6.87-6.81 (m, 1H), 6.80-6.75 (m, 1H), 6.72 (m, 1H), 5.34 (d, J = 7.1 Hz, 1H), 5.16 (dd, J = 10.2, 5.8 Hz, 1H), 5.04 (d, J = 5.8 Hz, 1H), 4.23 (qd, J = 7.2, 3.1 Hz, 2H), 3.80 (s, 3H), 3.14 (dd, J

= 12.4, 10.2 Hz, 1H), 1.91 (ddq, J = 12.4, 7.1, 6.6 Hz, 1H), 1.25 (t, J = 7.2 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl₃) : 167.8, 160.0, 139.2, 130.1, 120.2, 114.1, 113.0, 98.0, 89.4, 69.6, 62.2, 55.2, 48.0, 39.4, 15.4, 13.8 ppm;

FTIR (cm^-1): 3442, 2980, 2927, 1746, 1555, 1456, 1375, 1264, 1220, 1123, 1047, 1025, 702; HRMS (EI) m/z calcd. for C16H21NO7 [M]⁺ 339.1318, found 339.1315;

HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 26.8 min, t_R (major) = 58.1 (min).

Recovery 129i

For recovery alcohol (129i): Spectroscopic data are in agreement with racemic substrate 129i. Isolated yield: 35%.

[]^25.5D = +67.7 (c = 1.0 in CHCl3). The enantiomeric excess (84% ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 13.5 min, tR (major) = 28.9 (min).

Compound 125j

96% ee, []^25.5D = -57.9 (c = 1.0 in CHCl3); Dark yellow liquid; Rf

= 0.23 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3):

7.42 (d, J = 1.8 Hz, 1H), 6.33 (dd, J = 3.2, 1.8 Hz, 1H), 6.24 (d, J = 3.2 Hz, 1H), 5.28 (dd, J = 9.2, 6.8 Hz, 1H), 5.24 (d, J = 6.8, 1H), 5.00 (d, J = 5.3 Hz, 1H), 4.28-4.21 (m, 2H), 3.33 (dd, J = 11.9, 9.2 Hz, 1H), 2.04 (ddq, J = 11.9, 6.6, 5.3 Hz, 1H), 1.25 (t, J = 7.2 Hz, 3H), 0.93 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 167.9, 149.9, 142.7, 110.4, 109.5, 98.0, 86.4, 68.1, 62.3, 41.9, 37.3, 15.6, 13.8 ppm; FTIR (cm^-1): 3455, 2980, 2923, 1746, 1641, 1555, 1371, 1233, 1123, 1018, 742; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR (minor) = 17.0 min, tR (major)

= 38.1 (min).

Recovery 129j

For recovery alcohol (129j): Spectroscopic data are in agreement with racemic substrate 129j. Isolated yield: 31%. []^25.5D = +172.8 (c

= 1.0 in CHCl3). The enantiomeric excess (86% ee) was determined by HPLC with AS-H column, and following the condition: 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 74.0 min, tR

(major) = 128.9 (min).

Compound 125k

95% ee, []^25.5D = -66.4 (c = 1.0 in CHCl₃); Sticky liquid; R_f = 0.23 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃):

7.28 (d, J = 5.2 Hz, 1H), 6.96 (dd, J = 5.2, 3.4 Hz, 1H), 6.92 (d, J = 3.4 Hz, 1H), 5.34 (d, J = 7.4 Hz, 1H), 5.13 (dd, J = 10.0, 5.7 Hz, 1H), 5.03 (d, J = 5.7 Hz, 1H), 4.28-4.19 (m, 2H), 4.02 (s, 1H), 3.56 (dd, J = 12.0, 10.0 Hz, 1H),

1.90 (ddq, J = 12.0, 7.4, 6.6 Hz), 1.25 (t, J = 7.1 Hz, 3H), 0.97 (d, J =6.6 Hz, 3H) ppm;

13C NMR (100 MHz, CDCl₃) : 167.7, 140.6, 127.1, 127.0, 125.4, 97.8, 90.2, 69.2, 62.3, 43.6, 40.7, 15.5, 13.8 ppm; FTIR (cm^-1): 3442, 2976, 2910, 1746, 1555, 1375, 1228, 1125, 1064, 1020, 854, 707; HRMS (ESI) m/z calcd. for C13H17NO6NaS [M+Na]⁺ 338.0674, found 338.0667; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR

(minor) = 22.1 min, t_R (major) = 41.0 (min).

Recovery 129k

For recovery alcohol (129k): Spectroscopic data are in agreement with racemic substrate 129k. Isolated yield: 31%. []^25.5D = +145.3 (c

= 1.0 in CHCl3). The enantiomeric excess (85% ee) was determined by HPLC with AD-H column, and following the condition: 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 28.2 min, t_R (major) = 33.5 (min).

Compound 125l

94% ee, []^25.5D = -74.2 (c = 1.0 in CHCl3); White solid; Rf = 0.19 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3): 7.88-7.80 (m, 3H), 7.63 (s, 1H), 7.52-7.47 (m, 2H), 7.33 (dd, J = 8.5, 1.7 Hz, 1H), 5.39 (d, J = 7.6 Hz, 1H), 5.29 (dd, J = 10.1, 5.8 Hz, 1H), 5.11 (d, J = 5.8 Hz, 1H), 4.25 (qd, J = 7.1, 3.4 Hz, 2H), 3.82 (s, 1H), 3.35 (dd, J = 12.4, 10.1 Hz, 1H), 2.06 (ddq, J = 12.4, 7.6, 6.6 Hz, 1H), 1.25 (t, J = 7.1 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 167.8, 134.8,

133.3, 133.0, 129.2, 127.9, 127.8, 127.7, 126.6, 126.3, 124.6, 98.1, 89.5, 69.4, 62.3, 48.3, 39.2, 15.5, 13.8 ppm; HRMS (ESI) m/z calcd. for C19H21NO6Na [M+Na]⁺ 382.1267, found 382.1271； FTIR (cm^-1): 3451, 2976, 2927, 1750, 1555, 1461, 1378, 1226, 1123, 1066, 1020, 748; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 23.5 min, tR (major) = 48.6 (min).

Recovery 129l

For recovery alcohol (129l): Spectroscopic data are in agreement with racemic substrate 129l. Isolated yield: 35%.

[]^25.5D = +24.5 (c = 1.0 in CHCl3). The enantiomeric excess (97% ee) was determined by HPLC with AD-H column, and following the condition:

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR

(minor) = 16.6 min, tR (major) = 53.5 (min).

Compound 125m

99% ee (major), []^25.5D = -96.6 (c = 1.0 in CHCl3); Pale yellow liquid; Rf = 0.23 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3): 7.38-7.27 (m, 5H), 6.51 (d, J = 15.7 Hz, 1H), 6.05 (dd, J = 15.7, 9.4 Hz, 1H), 5.26 (d, J = 6.2 Hz, 1H), 4.95 (d, J = 5.3 Hz, 1H), 4.87 (dd, J = 8.5, 5.3 Hz, 1H), 4.24 (qd, J = 7.1, 3.3 Hz, 2H), 2.93 (ddd, J = 9.4, 9.2, 8.5 Hz), 1.72 (ddq, J = 9.2, 6.8, 6.2 Hz, 1H), 1.26 (t, J = 7.1 Hz, 3H),

1.08 (d, J = 6.8 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 168.1, 136.1, 135.1, 128.6, 128.1, 126.5, 125.9, 97.9, 87.5, 67.7, 62.3, 46.2, 37.7, 16.2, 13.9 ppm; HRMS (ESI) m/z calcd. for C₁₇H₂₁NO₆Na [M+Na]⁺ 358.1267, found 358.1258； FTIR (cm^-1): 3455, 2976, 2923, 1746, 1553, 1373, 1224, 1125, 1066, 970, 751, 694;

HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: t_R (minor) = 21.5 min, t_R (major) = 40.8 (min).

Recovery 129m

For recovery alcohol (129m): Spectroscopic data are in agreement with racemic substrate 129m. Isolated yield: 36%.

[]^25.5D = +15.6 (c = 1.0 in CHCl3). The enantiomeric excess (70%

ee, major) was determined by HPLC with OD-H column, and following the condition: 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 33.4 min, tR (major) = 49.9 (min).

Compound 125n

96% ee, []^25.5D = -30.8 (c = 1.0 in CHCl₃); White solid; R_f = 0.28 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.35-7.32 (m, 3H), 7.27-7.25 (m, 3H), 7.19-7.18 (m, 2H), 6.91-6.89 (m, 2H), 5.59 (dd, J = 4.6, 4.6 Hz, 1H), 5.21 (dd, J = 9.4, 5.3 Hz, 1H), 5.01 (d, J = 5.3 Hz, 1H), 4.57 (d, J = 11.1 Hz, 1H), 4.34-4.17 (m, 4H), 3.73 (dd, J = 9.7, 9.4 Hz, 1H), 3.61 (dd, J = 9.7, 4.6 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl₃) : 167.4, 137.0, 136.6, 128.9, 128.2, 128.0, 127.8, 96.6, 86.4, 79.1, 73.6, 69.0, 62.4, 47.0, 29.7, 13.9 ppm; FTIR (cm^-1): 3442, 2923, 1739, 1555, 1452, 1367, 1224, 1110, 1077, 1012, 748, 702; HRMS (ESI) m/z calcd. for C₂₁H₂₃BrNO₇Na [M+Na]⁺ 424.1372, found 424.1375.; HPLC conditions: AD-H column, 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: t_R (minor) = 37.6 min, t_R (major) = 67.2 (min).

Recovery 129f

For recovery alcohol (129f): Spectroscopic data are in agreement with racemic substrate 129f. Isolated yield: 36%. The enantiomeric excess (91% ee) was determined by HPLC with OD-H column, and following the condition: 2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 9.7 min, tR (major) = 11.7 (min).

Compound 129e

95% ee, []^25.5D = +85.2 (c = 1.0 in CHCl₃); white solid; R_f = 0.49 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl3): 8.13 (s, 1H), 7.74 (s, 1H), 5.12 (d, J = 5.8 Hz, 1H), 4.33 (q, J = 7.1 Hz, 2H), 3.95 (s, 3H), 3.67 (dd, J = 5.8, 1.3 Hz, 1H), 1.30 (t, J = 7.1 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 169.9, 156.4, 148.9, 135.5, 133.8, 129.2, 119.2, 65.6, 63.3, 60.9, 14.0 ppm; FTIR (cm^-1): 3481, 2980, 1750, 1531, 1472, 1419, 1340, 1268, 1106, 987, 862, 751; HRMS (ESI) m/z calcd. for C13H13Br2NO6Na [M+Na]⁺ 459.9007, found 459.9002.; HPLC conditions: AD-H column, 2-propanol/n-hexane =

10/90, flow rate = 1.0 ml/min,  = 254 nm, retention time: tR (minor) = 12.2 min, tR

(major) = 19.1 (min).

Compound 131

>99% ee, []^25.5D = -100.8 (c = 0.5 in CHCl₃); White solid; R_f

= 0.34 (33% EtOAc in Hexanes); ¹H NMR (400 MHz, CDCl₃): 7.55 (d, J = 8.2 Hz, 2H), 7.13 (d, J = 8.2 Hz, 2H), 5.31 (dd, J = 8.8, 4.4 Hz, 1H), 5.26 (d, J = 4.4 Hz, 1H), 4.34 (q, J = 7.1 Hz, 2H), 3.52 (dd, J = 11.5, 8.8 Hz, 1H), 2.77 (dq, J = 11.5 , 6.7 Hz, 1H), 1.32 (t, J = 7.1 Hz, 3H), 1.23 (d, J = 6.7 Hz, 3H) ppm; ¹³C NMR (100 MHz, CDCl3) : 169.8, 165.8, 136.3, 132.8, 129.2, 122.8, 86.0, 73.8, 63.4, 46.6, 40.0, 14.1, 13.9 ppm; FTIR (cm^-1): 2985, 2923, 1761, 1649, 1555, 1489, 1224, 1180, 1141, 1104, 1073, 1012, 847, 819, 751, 724; HRMS (ESI) m/z calcd. for C15H16BrNO6Na [M+Na]⁺ 408.0059, found 408.0058.; Crystal data for 131 at 200 (2) K: C15H16BrNO6, M 386.20, Monoclinic, P 21, a = 12.3396 (6) Å , b = 6.1527 (3) Å , c = 12.6959 (6) Å , V = 930.11 (8) Å³, Z = 2, Dx = 1.379 Mg/m³,  = 2.236 mm^-1, 6673 reflections, 208 parameters, R = 0.0521, Rw

= 0.1123, flack parameter = 0.012 (13) for all data.; HPLC conditions: AD-H column,

2-propanol/n-hexane = 10/90, flow rate = 1.0 ml/min,  = 220 nm, retention time: tR

(minor) = 44.7 min, tR (major) = 109.8 (min).

在文檔中有機催化連鎖外消旋硝基丙烯醇動力學分割之探討 (頁 66-94)