Supporting Information

Cyanohydrin-Mediated Cyanation of Remote

Unactivated C(sp3)-H Bonds

Min Wanga, Leitao Huana, and Chen Zhu*,a,b

a
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road,
Suzhou, Jiangsu 215123, China
b
Key Laboratory of Synthesis Chemistry of Natural Substances, Shanghai Institute of
Organic Chemistry, Chinese Academy of Science, 345 Lingling Road, Shanghai
200032, China

Email: [email protected]

Table of Contents

1. General experimental details S2

2. General procedure for the C(sp3)-H bond cyanation S2
3. Survey of reaction conditions S2
4. Characterization of starting materials S4
5. Characterization of products S10
6. 1H, 13C, 19F NMR spectra S18
7. Mechanistic studies S94
1. General experimental details
All reactions were maintained under a nitrogen atmosphere unless otherwise stated.
Commercially available reagents were used without further purification. Infrared (FT-IR) spectra
were recorded on a BRUKER VERTEX 70, νmax in cm-1. 1H-NMR spectra were recorded on a
BRUKER AVANCE III HD (400 MHz) spectrometer. Chemical shifts are reported in ppm from
tetramethylsilane with the solvent resonance as internal standard (CDCl3: δ 7.26). Data are
reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quadruplet,
br = broad, m = multiplet), coupling constants (Hz) and integration. 13C-NMR spectra were
recorded on a BRUKER AVANCE III HD (100 MHz) spectrometer with complete proton
decoupling. Chemical shifts are reported in ppm from tetramethylsilane with the solvent resonance
as the internal standard (CDCl3: δ 77.16). 19F-NMR spectra were recorded on a BRUKER
AVANCE III HD (376 MHz) spectrometer. Mass spectra were measured with an Agilent
Technologies 6120 Quadrupole LC/MS. High resolution mass spectrometry (HRMS) were
measured with a GCT PremierTM and BRUKER micrOTF-Q III. Melting points were measured
using INESA WRR and values are uncorrected.

2. General procedure for the C(sp3)-H bond cyanation

Cyanohydrin 1 (0.3 mmol, 1 equiv.), photocatalyst Ir{[dF(CF3)ppy]2(dtbbpy)}PF6 (10.1 mg,
9.0 µmol, 3 mol %), K2S2O8 (178.4 mg, 0.66 mmol, 2.2 equiv.), and TBAC (27.4 mg, 0.12 mmol,
0.4 equiv.) were loaded in a reaction vial which was subjected to evacuation/ flushing with N2 for
three times. PhCF3/H2O (3 mL/ 0.3 mL) was added to the mixture via syringe and the reaction was
irradiated with 14 W blue LEDs. After the reaction completion, the reaction mixture was extracted
with ethyl acetate (3 x 10 mL). The combined organic extracts were washed by brine, dried over
MgSO4, filtered, concentrated in vacuo, and purified by flash column chromatography on silica
gel (eluent: ethyl acetate/ petroleum ether) to give the desired product 2.

3. Survey of reaction conditions

Catalyst Oxidant Additive Solvent Time Yield
(%)
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.2eq) PhCF3/H2O(1/0.1) 5h 70
Ir(ppy)3(3%) K2S2O8(2.2eq) Bu4NCl(0.2eq) PhCF3/H2O(1/0.1) 23h trace
Ir-F002(3%) K2S2O8(2.2eq) Bu4NCl(0.2eq) PhCF3/H2O(1/0.1) 23h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 13h 82
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) CH3CN/H2O(1/0.1) 23h 26
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) DCE/H2O(1/0.1) 23h 71
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) Toluene/H2O(1/0.1) 23h 50
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) THF/H2O(1/0.1) 23h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3 23h 67
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) H2O 23h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) DMF/H2O(1/0.1) 23h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) Dioxane/H2O(1/0.1) 23h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCl/H2O(1/0.1) 24h 69
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(0.8/0.2) 24h 74
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(0.7/0.3) 24h 76
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 24h 81
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.5) 24h 75
Ir-Foo1(3%) H2O2(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h trace
Ir-Foo1(3%) O2(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h ND
Ir-Foo1(3%) TBHP(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h trace
Ir-Foo1(3%) (NH4)2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h 79
Ir-Foo1(3%) m-CPBA(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h trace
Ir-Foo1(3%) DTBP(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h trace
Ir-Foo1(3%) PIDA(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 23h 10
Ir-Foo1(3%) Na2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 17h 75
Ir-Foo1(3%) none Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 17h ND
Ir-Foo1(3%) K2S2O8(3.0eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 25h 81
Ir-Foo1(3%) K2S2O8(4.0eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 25h 80
Ir-Foo1(3%) K2S2O8(1.5eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 25h 64
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NF(0.4eq) PhCF3/H2O(1/0.1) 19h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NBr(0.4eq) PhCF3/H2O(1/0.1) 19h 62
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NH2PO4 (0.4eq) PhCF3/H2O(1/0.1) 19h 50
Ir-Foo1(3%) K2S2O8(2.2eq) none PhCF3/H2O(1/0.1) 19h trace
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.2eq) PhCF3/H2O(1/0.1) 19h 68
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.5eq) PhCF3/H2O(1/0.1) 19h 74
Ir-Foo1(3%) K2S2O8(2.2eq) Bu4NCl(0.8eq) PhCF3/H2O(1/0.1) 19h 70
Ir-Foo1(1%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 12h 41
Ir-Foo1(5%) K2S2O8(2.2eq) Bu4NCl(0.4eq) PhCF3/H2O(1/0.1) 12h 84
4. Characterization of starting materials
1a: yellow oil, (10 mmol, 1.62 g, 80%). 1H NMR (400 MHz, CDCl3) δ
7.52-7.48 (m, 2H), 7.42 -7.33 (m, 3H), 4.05 (s, 1H), 2.07-1.88 (m, 2H),
1.58-1.47 (m, 1H), 1.44-1.34 (m, 1H), 1.25-1.15 (m, 1H), 0.89-0.84 (m,
6H); 13C NMR (100 MHz, CDCl3) δ 140.0, 129.0, 128.8, 125.0, 120.9,
74.7, 41.6, 33.0, 27.8, 22.4, 22.4. FT-IR: ν (cm-1) 3413, 2957, 2929, 2871, 2244, 1493, 1450, 1369,
1267. HRMS [ESI] calcd for C13H17NNaO [M+Na]+ 226.1202, found 226.1208.

1b: white solid, (2 mmol, 0.50 g, 90%), m.p. 97-98 oC. 1H NMR (400
MHz, CDCl3) δ 7.66-7.57 (m, 6H), 7.49-7.43 (m, 2H), 7.41-7.35 (m,
1H), 3.28 (br, 1H), 2.15-2.06 (m, 1H), 2.06-1.96 (m, 1H), 1.63-1.53
(m, 1H), 1.52-1.42 (m, 1H), 1.36-1.28 (m, 1H), 0.92-0.87 (m, 6H);
13C NMR (100 MHz, CDCl ) δ 141.5, 139.6, 138.5, 128.4, 127.3, 127.0, 126.6, 124.9, 120.4, 74.2,
3

41.1, 32.6, 27.4, 21.9, 21.9. FT-IR: ν (cm-1) 3402, 2960, 2926, 2871, 2256, 1508, 1486, 1384,
1267. HRMS [ESI] calcd for C19H21NNaO [M+Na]+ 302.1515, found 302.1511.

1c: yellow solid, (2 mmol, 0.30 g, 64%), m.p. 41-42 oC. 1H NMR
(400 MHz, CDCl3) δ 7.47-7.42 (m, 2H), 6.93-6.88 (m, 2H), 3.81 (s,
3H), 3.16 (br, 1H), 2.09-2.00 (m, 1H), 1.98-1.88 (m, 1H), 1.60-1.48
(m, 1H), 1.46-1.35 (m, 1H), 1.24-1.14 (m, 1H), 0.88 (d, J = 6.4 Hz,
3H), 0.86 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 159.3, 131.7, 125.8, 120.6, 113.6,
73.8, 54.9, 41.0, 32.6, 27.3, 21.9, 21.9. FT-IR: ν (cm-1) 3421, 2956, 2870, 2840, 2244, 1610, 1511,
1466, 1368, 1251. HRMS [ESI] calcd for C14H19NNaO2 [M+Na]+ 256.1308, found 256.1301.

1d: yellow solid, (2 mmol, 0.30 g, 69%), m.p. 30-31 oC. 1H NMR (400
MHz, CDCl3) δ 7.45-7.41 (m, 2H), 7.24-7.20 (m, 2H), 2.87 (br, 1H),
2.38 (s, 3H), 2.10-2.01 (m, 1H), 1.99-1.90 (m, 1H), 1.60-1.49 (m, 1H),
1.48-1.37 (m, 1H), 1.28-1.17 (m, 1H), 0.88 (d, J = 6.8 Hz, 3H), 0.86 (d,
J = 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 138.5, 136.6, 129.0, 124.4, 120.5, 74.2, 41.0, 32.6,
27.4, 21.9, 21.8, 20.6. FT-IR: ν (cm-1) 3414, 2956, 2927, 2870, 2244, 1614, 1513, 1468, 1386,
1229. HRMS [ESI] calcd for C14H19NNaO [M+Na]+ 240.1359, found 240.1361.

1e: yellow oil, (2 mmol, 0.51 g, 89%). 1H NMR (400 MHz, CDCl3)
δ 7.54-7.49 (m, 2H), 7.25-7.20 (m, 2H), 4.46 (s, 1H), 2.05-1.87 (m,
2H), 1.57-1.46 (m, 1H), 1.42-1.31 (m, 1H), 1.25-1.14 (m, 1H),
0.85 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 149.0 (q, JC-F = 1.7
Hz), 138.1, 126.1, 120.5, 120.1, 119.9 (q, JC-F = 256.1 Hz), 73.5, 41.2, 32.3, 27.2, 21.7, 21.6. 19F
NMR (376 MHz, CDCl3) δ -58.1 (s). FT-IR: ν (cm-1) 3412, 2960, 2933, 2874, 2245, 1509, 1470,
1370, 1255, 1211. HRMS [ESI] calcd for C14H17F3NO2 [M+H-HCN]+ 261.1097, found 261.1116.

1f: yellow oil, (2 mmol, 0.46 g, 85%). 1H NMR (400 MHz, CDCl3)
δ 7.67-7.59 (m, 4H), 4.68 (s, 1H), 2.06-1.90 (m, 2H), 1.58-1.46 (m,
1H), 1.41-1.30 (m, 1H), 1.26-1.15 (m, 1H), 0.86 (d, J = 5.2 Hz, 3H),
0.84 (d, J = 5.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 143.3 (d, JC-F = 0.9 Hz), 130.7 (q, JC-F =
32.5 Hz), 125.2 (q, JC-F = 3.7 Hz), 125.0, 123.3 (q, JC-F = 270.6 Hz), 120.0, 73.6, 41.2, 32.2, 27.2,
21.7, 21.6. 19F NMR (376 MHz, CDCl3) δ -62.8 (s). FT-IR: ν (cm-1) 3421, 2960, 2873, 2247, 1621,
1469, 1412, 1389, 1242. HRMS [ESI] calcd for C14H16F3NNaO [M+Na]+ 294.1076, found
294.1063.

1g: yellow oil, (1 mmol, 0.12 g, 55%). 1H NMR (400 MHz, CDCl3) δ
7.70-7.63 (m, 4H), 7.12 (br, 1H), 2.05-1.89 (m, 2H), 1.57-1.46 (m,
1H), 1.40-1.29 (m, 1H), 1.28-1.17 (m, 1H), 0.85 (d, J = 4.0 Hz, 3H),
0.84 (d, J = 4.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 145.3, 132.6,
125.9, 120.2, 118.1, 112.6, 73.9, 41.7, 32.7, 27.7, 22.3, 22.3. FT-IR: ν (cm-1) 3409, 2957, 2829,
2871, 2233, 1610, 1504, 1469, 1406, 1367, 1229. HRMS [ESI] calcd for C14H16N2NaO [M+Na]+
251.1155, found 251.1141.

1h: yellow oil, (2 mmol, 0.27 g, 61%). 1H NMR (400 MHz, CDCl3) δ
7.49-7.43 (m, 2H), 7.10-7.03 (m, 2H), 4.13 (s, 1H), 2.04-1.85 (m, 2H),
1.57-1.45 (m, 1H), 1.40-1.29 (m, 1H), 1.21-1.10 (m, 1H), 0.85 (t, J =
6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 162.4 (d, JC-F = 246.8 Hz),
135.3 (d, JC-F = 3.2 Hz), 126.4 (d, JC-F = 8.4 Hz), 120.3, 115.2 (d, JC-F = 21.7 Hz), 73.6, 41.2, 32.4,
27.3, 21.9, 21.8. 19F NMR (376 MHz, CDCl3) δ -112.6 (s). FT-IR: ν (cm-1) 3421, 2957, 2931,
2871, 2244, 1678, 1597, 1509, 1468, 1368, 1231. HRMS [ESI] calcd for C13H16FNNaO [M+Na]+
244.1108, found 244.1112.

1i: yellow oil, (2 mmol, 0.38 g, 80%). 1H NMR (400 MHz, CDCl3) δ
7.48-7.43 (m, 2H), 7.40-7.35 (m, 2H), 3.37 (br, 1H), 2.06-1.97 (m,
1H), 1.96-1.87 (m, 1H), 1.59-1.47 (m, 1H), 1.43-1.31 (m, 1H),
1.25-1.14 (m, 1H), 0.86 (t, J = 6.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 138.0, 134.4, 128.4, 126.0, 120.1, 73.5, 41.1, 32.3, 27.3, 21.9, 21.8. FT-IR: ν (cm-1)
3410, 2957, 2929, 2871, 2247, 1493, 1402, 1369, 1217. HRMS [ESI] calcd for C13H16ClNNaO
[M+Na]+ 260.0813, found 260.0818.

1j: yellow oil, (2 mmol, 0.46 g, 82%). 1H NMR (400 MHz, CDCl3) δ
7.52-7.47 (m, 2H), 7.36-7.31 (m, 2H), 4.22 (s, 1H), 2.02-1.83 (m,
2H), 1.56-1.44 (m, 1H), 1.39-1.27 (m, 1H), 1.21-1.10 (m, 1H), 0.84 (t,
J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 138.5, 131.4, 126.2,
122.6, 120.0, 73.6, 41.1, 32.3, 27.3, 21.9, 21.9. FT-IR: ν (cm-1) 3409, 2956, 2928, 2870, 2247,
1591, 1488, 1368, 1266. HRMS [ESI] calcd for C13H16BrNNaO [M+Na]+ 304.0307, found
304.0307.

1k: yellow oil, (2 mmol, 0.35 g, 81%). 1H NMR (400 MHz, CDCl3) δ
7.36-7.33 (m, 1H), 7.33-7.26 (m, 2H), 7.19-7.15 (m, 1H), 4.06 (s, 1H),
2.39 (s, 3H), 2.07-1.89 (m, 2H), 1.60-1.49 (m, 1H), 1.47-1.36 (m, 1H),
1.28-1.17 (m, 1H), 0.89 (t, J = 6.8 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 139.6, 138.1, 129.2, 128.2, 125.1, 121.6, 120.5, 74.2, 41.1, 32.5, 27.4, 21.9, 21.9, 21.0.
FT-IR: ν (cm-1) 3417, 2956, 2928, 2870, 2244, 1608, 1468, 1368, 1448, 1368, 1247. HRMS [ESI]
calcd for C14H19NNaO [M+Na]+ 240.1359, found 240.1355.

1l: yellow oil, (2 mmol, 0.30 g, 63%). 1H NMR (400 MHz, CDCl3) δ
7.54-7.51 (m, 1H), 7.43-7.37 (m, 1H), 7.37-7.28 (m, 2H), 3.32 (br,
1H), 2.06-1.88 (m, 2H), 1.60-1.48 (m, 1H), 1.44-1.33 (m, 1H),
1.29-1.18 (m, 1H), 0.92-0.82 (m, 6H); 13C NMR (100 MHz, CDCl3) δ
141.6, 134.4, 129.6, 128.8, 124.7, 122.7, 120.0, 73.6, 41.2, 32.4, 27.3, 21.9, 21.8. FT-IR: ν (cm-1)
3414, 2957, 2929, 2871, 2246, 1707, 1597, 1470, 1387, 1243. HRMS [ESI] calcd for
C13H16ClNNaO [M+Na]+ 260.0813, found 260.0824.

1m: yellow oil, (2 mmol, 0.41 g, 86%). 1H NMR (400 MHz, CDCl3) δ
7.72-7.66 (m, 1H), 7.43-7.38 (m, 1H), 7.36-7.28 (m, 2H), 3.79 (br, 1H),
2.37-2.27 (m, 1H), 2.18-2.08 (m, 1H), 1.62-1.51 (m, 1H), 1.48-1.37 (m,
1H), 1.36-1.24 (m, 1H), 0.88 (t, J = 6.8 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 135.7, 130.8, 130.5, 129.6, 127.0, 126.7, 119.4, 71.7, 36.9, 32.0, 27.3, 22.0, 21.9. FT-IR:
ν (cm-1) 3394, 2957, 2931, 2871, 2246, 1572, 1469, 1386, 1223. HRMS [ESI] calcd for
C13H16ClNNaO [M+Na]+ 260.0813, found 260.0826.

1n: yellow oil, (2 mmol, 0.20 g, 35%). 1H NMR (400 MHz, CDCl3) δ
7.72-7.68 (m, 1H), 7.62-7.58 (m, 1H), 7.38-7.32 (m, 1H), 7.23-7.17 (m,
1H), 4.26 (s, 1H), 2.40-2.30 (m, 1H), 2.19-2.09 (m, 1H), 1.60-1.49 (m,
1H), 1.46-1.36 (m, 1H), 1.34-1.24 (m, 1H), 0.88 (t, J = 6.4 Hz, 6H); 13C
NMR (100 MHz, CDCl3) δ 136.9, 134.5, 129.8, 127.3, 119.6, 119.4, 73.0, 37.0, 32.1, 27.3, 22.0,
21.9. FT-IR: ν (cm-1) 3394, 2957, 2930, 2870, 2245, 1568, 1466, 1368, 1222. HRMS [ESI] calcd
for C13H16BrNNaO [M+Na]+ 304.0307, found 304.0305.

1o: yellow solid, (0.5 mmol, 0.068 g, 50%), m.p. 52-53oC.

1H NMR (400 MHz, CDCl ) δ 7.49-7.44 (m, 2H), 7.01-6.96
3

(m, 2H), 4.67-4.63 (m, 2H), 3.06 (br, 1H), 2.10-2.00 (m,
1H), 1.98-1.89 (m, 1H), 1.87-1.84 (m, 3H), 1.60-1.49 (m,
1H), 1.47-1.36 (m, 1H), 1.24-1.16 (m, 1H), 0.87 (t, J = 7.2
Hz, 6H); C NMR (100 MHz, CDCl3) δ 157.8, 132.1, 125.8, 120.4, 114.6, 83.7, 74.0, 73.2, 56.0,
13

41.0, 32.6, 27.3, 21.9, 21.8, 3.2. FT-IR: ν (cm-1) 3402, 2955, 2923, 2869, 2244, 1733, 1601, 1509,
1467, 1370, 1227. HRMS [ESI] calcd for C17H21NNaO2 [M+Na]+ 294.1465, found 294.1453.

1p: yellow solid, (1 mmol, 0.13 g, 50%), m.p. 39-40 oC. 1H NMR
(400 MHz, CDCl3) δ 7.47-7.42 (m, 2H), 6.96-6.90 (m, 2H),
6.10-5.99 (m, 1H), 5.45-5.38 (m, 1H), 5.33-5.28 (m, 1H),
4.57-4.52 (m, 2H), 3.03 (br, 1H), 2.10-2.00 (m, 1H), 1.98-1.88
(m, 1H), 1.60-1.48 (m, 1H), 1.46-1.35 (m, 1H), 1.25-1.15 (m,
1H), 0.90-0.83 (m, 6H); C NMR (100 MHz, CDCl3) δ 158.6, 132.4, 131.7, 125.8, 120.5, 117.5,
13

114.4, 74.0, 68.4, 41.0, 32.6, 27.3, 21.9, 21.9. FT-IR: ν (cm-1) 3398, 2956, 2926, 2869, 2245, 1608,
1509, 1457, 1385, 1247. HRMS [ESI] calcd for C16H21NNaO2 [M+Na]+ 282.1465, found
282.1472.

1q: yellow oil, (2 mmol, 0.32 g, 77%). 1H NMR (400 MHz, CDCl3) δ 3.29
(br, 1H), 1.94-1.87 (m, 1H), 1.86-1.77 (m, 3H), 1.76-1.61 (m, 3H),
1.59-1.49 (m, 2H), 1.46-1.32 (m, 2H), 1.29-1.09 (m, 5H), 0.89 (d, J = 6.8
Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 120.6, 75.2, 45.0, 34.7, 32.0, 27.6,
27.0, 26.0, 25.5, 25.4, 25.4, 21.9. FT-IR: ν (cm-1) 3443, 2954, 2930, 2856, 2238, 1717, 1468, 1386,
1245. HRMS [ESI] calcd for C13H23NNaO [M+Na]+ 232.1672, found 232.1671.

1r: yellow oil, (2 mmol, 0.48 g, 99%). 1H NMR (400 MHz, CDCl3) δ
7.53-7.48 (m, 2H), 7.42-7.33 (m, 3H), 3.58 (br, 1H), 2.08-1.90 (m, 2H),
1.71-1.58 (m, 5H), 1.46-1.34 (m, 1H), 1.27-1.08 (m, 5H), 0.93-0.79 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 139.5, 128.5, 128.3, 124.5, 120.4,
74.3, 40.7, 36.9, 32.6, 32.6, 31.1, 26.0, 25.7. FT-IR: ν (cm-1) 3413, 2922, 2851, 2244, 1492, 1449,
1376, 1272. HRMS [ESI] calcd for C16H21NNaO [M+Na]+ 266.1515, found 266.1502.

1s: yellow oil, (0.7 mmol, 0.15 g, 95%). 1H NMR (400 MHz, CDCl3) δ
7.53-7.49 (m, 2H), 7.42-7.33 (m, 3H), 3.66 (s, 1H), 1.96-1.89 (m, 1H),
1.88-1.76 (m, 2H), 1.70-1.49 (m, 5H), 1.29-1.08 (m, 3H), 1.05-0.85 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 140.1, 128.4, 128.3, 124.4, 120.8,
73.5, 50.2, 33.6, 33.6, 33.4, 25.6, 25.6. FT-IR: ν (cm-1) 3410, 2922, 2851, 2246, 1698, 1449, 1387,
1448, 1259. HRMS [ESI] calcd for C15H19NNaO [M+Na]+ 252.1359, found 252.1370.

1t (1:1): yellow oil, (2 mmol, 0.15 g, 37%). 1H NMR (400 MHz, CDCl3) δ
7.55-7.50 (m, 4H, two isomers), 7.42-7.33 (m, 6H, two isomers), 3.69 (br,
2H, two isomers), 2.09-2.03 (m, 1H, one isomer), 1.99-1.93 (m, 1H, one
isomer), 1.89-1.83 (m, 1H, one isomer), 1.83-1.76 (m, 1H, one isomer),
1.68-1.53 (m, 2H, two isomers), 1.47-1.35 (m, 1H, one isomer), 1.33-1.25 (m, 1H, one isomer),
1.24-1.11 (m, 2H, two isomers), 0.98 (d, J = 6.8 Hz, 3H, one isomer), 0.87-0.81 (m, 6H, two
isomers), 0.80 (t, J = 7.6 Hz, 3H, one isomer); 13C NMR (100 MHz, CDCl3) δ 140.1 (overlap, two
isomers), 128.5 & 128.5 (two isomers), 128.3 (overlap, two isomers), 124.5 & 124.5 (two
isomers), 120.9 & 120.8 (two isomers), 73.9 & 73.6 (two isomers), 49.4 & 49.3 (two isomers),
30.7 & 30.3 (two isomers), 29.8 (overlap, two isomers), 19.8 & 19.6 (two isomers), 10.5 & 10.5
(two isomers). FT-IR: ν (cm-1) 3408, 2962, 2930, 2876, 2246, 1493, 1450, 1381, 1255. HRMS
[ESI] calcd for C13H18NO [M+H-HCN]+ 177.1274, found 177.1288.

1u: yellow oil, (1 mmol, 0.23 g, 92%). 1H NMR (400 MHz, CDCl3)
δ 7.59-7.53 (m, 2H), 7.49-7.41 (m, 3H), 7.39-7.33 (m, 2H),
7.31-7.25 (m, 1H), 7.24-7.19 (m, 2H), 3.93 (s, 1H), 2.73-2.65 (m,
2H), 2.19-2.10 (m, 1H), 2.09-2.01 (m, 1H), 1.99-1.88 (m, 1H),
1.83-1.70 (m, 1H); C NMR (100 MHz, CDCl3) δ 140.9, 139.4, 128.6, 128.4, 128.1, 128.0, 125.7,
13

124.6, 120.5, 74.0, 42.5, 34.8, 25.4. FT-IR: ν (cm-1) 3420, 3027, 2924, 2860, 2245, 1602, 1494,
1450, 1387, 1217. HRMS [ESI] calcd for C17H17NNaO [M+Na]+ 274.1202, found 274.1215.
 1v: yellow oil, (1.5 mmol, 0.15 g, 38%). 1H NMR (400 MHz,
CDCl3) δ 7.54-7.49 (m, 2H), 7.44-7.36 (m, 3H), 7.12-7.07 (m,
2H), 7.05-7.01 (m, 2H), 3.22 (s, 1H), 2.66-2.53 (m, 2H), 2.33 (s,
3H), 2.14-1.95 (m, 2H), 1.92-1.79 (m, 1H), 1.75-1.62 (m, 1H);
13C NMR (100 MHz, CDCl ) δ 139.3, 137.7, 135.0, 128.6, 128.4, 127.8, 124.5, 120.3, 74.0, 42.5,
3

34.3, 25.5, 20.5. FT-IR: ν (cm-1) 3420, 3022, 2923, 2861, 2244, 1515, 1449, 1378, 1216. HRMS
[ESI] calcd for C18H19NNaO [M+Na]+ 288.1359, found 288.1370.

1w: yellow oil, (1 mmol, 0.20 g, 60%). 1H NMR (400 MHz,

CDCl3) δ 7.52-7.46 (m, 2H), 7.42-7.36 (m, 3H), 7.16-7.10
(m, 4H), 3.66 (s, 1H), 2.68-2.55 (m, 2H), 2.12-1.93 (m,
2H), 1.92-1.80 (m, 1H), 1.75-1.62 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 147.1 (q, JC-F = 1.8 Hz), 139.5, 139.3,
129.1, 128.7, 128.4, 124.4, 120.5, 120.3, 120.1 (q, JC-F = 254.9 Hz), 73.9, 42.3, 34.0, 25.3. 19F
NMR (376 MHz, CDCl3) δ -57.9 (s). FT-IR: ν (cm-1) 3420, 2954, 2867, 2245, 1509, 1450, 1376,
1254. HRMS [ESI] calcd for C18H16F3NNaO2 [M+Na]+ 358.1025, found 358.1038.

1x: yellow oil, (1 mmol, 0.18 g, 88%). 1H NMR (400 MHz, CDCl3) δ
7.57-7.51 (m, 2H), 7.40-7.29 (m, 3H), 5.66 (br, 1H), 3.49-3.41 (m, 1H),
3.41-3.35 (m, 1H), 3.32 (s, 3H), 2.19-2.08 (m, 1H), 2.04-1.87 (m, 2H),
1.79-1.66 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 140.0, 128.2, 128.2,
124.4, 120.7, 73.2, 71.6, 58.0, 41.6, 24.5. FT-IR: ν (cm-1) 3406, 3291, 2930, 2873, 2833, 2240,
1734, 1449, 1389, 1226. HRMS [ESI] calcd for C12H15NNaO2 [M+Na]+ 228.0995, found
228.1001.

1y: yellow oil, (2 mmol, 0.30 g, 73%). 1H NMR (400 MHz, CDCl3) δ
7.60-7.55 (m, 2H), 7.43-7.32 (m, 3H), 5.70 (s, 1H), 4.09-4.02 (m, 1H),
3.77-3.71 (m, 1H), 3.66-3.50 (m, 2H), 2.33-2.24 (m, 1H), 2.13-2.07 (m,
1H), 1.25 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 139.6,
128.3, 128.2, 124.3, 120.3, 74.3, 67.7, 66.9, 41.9, 14.5. FT-IR: ν (cm-1) 3391, 2977, 2932, 2874,
2241, 1491, 1451, 1379, 1200. HRMS [ESI] calcd for C12H15NNaO2 [M+Na]+ 228.0995, found
228.0987.

1z: yellow oil, (2 mmol, 0.40 g, 92%). 1H NMR (400 MHz, CDCl3)
δ 7.52-7.48 (m, 2H), 7.42-7.33 (m, 3H), 3.88 (br, 1H), 2.06-1.97 (m,
1H), 1.96-1.87 (m, 1H), 1.55-1.41 (m, 1H), 1.35-1.19 (m, 7H), 0.88
(t, J = 6.4Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 139.5, 128.5,
128.3, 124.5, 120.4, 74.1, 43.1, 31.0, 28.4, 23.7, 22.0, 13.6. FT-IR: ν (cm-1) 3422, 2955, 2929,
2859, 2244, 1710, 1450, 1375, 1259. HRMS [ESI] calcd for C14H19NNaO [M+Na]+ 240.1359,
found 240.1345.
 3: yellow oil, (1 mmol, 0.23 g, 94%). 1H NMR (400 MHz, CDCl3)
δ 7.38-7.32 (m, 2H), 7.30-7.22 (m, 3H), 3.25 (s, 1H), 2.73 (t, J =
7.2 Hz, 2H), 2.01-1.87 (m, 2H), 1.87-1.70 (m, 4H), 1.67-1.57 (m,
1H), 1.51-1.37 (m, 2H), 0.97 (d, J = 6.8 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ 140.9, 128.0, 128.0, 125.6, 121.0, 71.7, 38.9, 37.5, 35.0, 32.2, 27.5, 25.1, 22.0,
22.0. FT-IR: ν (cm-1) 3435, 2955, 2929, 2869, 2239, 1604, 1497, 1454, 1387, 1265. HRMS [ESI]
calcd for C16H23NNaO [M+Na]+ 268.1672, found 268.1683.

4: yellow oil, (1 mmol, 0.18 g, 91%). 1H NMR (400 MHz, CDCl3) δ

3.22-3.12 (m, 1H), 1.79-1.65 (m, 4H), 1.62-1.46 (m, 3H), 1.45-1.36
(m, 2H), 1.35-1.27 (m, 4H), 0.93-0.86 (m, 9H); 13C NMR (100 MHz,
CDCl3) δ 121.1, 71.8, 39.5, 37.5, 32.2, 31.1, 27.5, 23.1, 21.9, 21.9, 13.4. FT-IR: ν (cm-1) 3440,
2956, 2929, 2871, 2240, 1717, 1468, 1386, 1270. HRMS [ESI] calcd for C12H23NNaO [M+Na]+
220.1672, found 220.1679.

5: yellow oil, (2 mmol, 0.44 g, 96%). 1H NMR (400 MHz, CDCl3)

δ 7.33-7.27 (m, 2H), 7.24-7.16 (m, 3H), 2.69 (t, J = 7.6 Hz, 2H),
2.53 (br, 1H), 1.96-1.84 (m, 2H), 1.82-1.66 (m, 4H), 1.55-1.43
(m, 2H), 1.42-1.32 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 140.8, 128.0,
127.9, 125.6, 120.9, 71.7, 39.4, 39.0, 34.9, 25.5, 25.1, 22.0, 13.4. FT-IR: ν (cm-1) 3445, 2956,
2932, 2866, 2238, 1716, 1604, 1558, 1455, 1339, 1260. HRMS [ESI] calcd for C15H21NNaO
[M+Na]+ 254.1515, found 254.1509.

6: yellow oil, (2 mmol, 0.29 g, 86%). 1H NMR (400 MHz, CDCl3) δ 3.80
(br, 1H), 1.72-1.60 (m, 4H), 1.57-1.42 (m, 3H), 1.41-1.24 (m, 2H), 0.92 (t,
J = 7.2 Hz, 3H), 0.85 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ
121.0, 71.6, 41.5, 37.4, 32.1, 27.4, 21.9, 21.8, 16.7, 13.3. FT-IR: ν (cm-1) 3438, 2959, 2935, 2874,
2239, 1597, 1468, 1386, 1252. HRMS [ESI] calcd for C10H19NNaO [M+Na]+ 192.1359, found
192.1362.

7: yellow oil, (2 mmol, 0.56 g, 99%). 1H NMR (400 MHz,

CDCl3) δ 7.69-7.65 (m, 2H), 7.51-7.44 (m, 3H), 7.39-7.34 (m,
2H), 7.30-7.24 (m, 3H), 4.20 (br, 1H), 3.77-3.73 (m, 1H),
3.68-3.60 (m, 1H), 3.60-3.55 (m, 1H), 2.79 (t, J = 7.6 Hz, 2H),
2.06-1.98 (m, 2H); C NMR (100 MHz, CDCl3) δ 141.6, 136.1, 129.5, 128.9, 128.6, 128.5, 126.1,
13

125.5, 120.3, 77.5, 73.5, 70.9 (t, JC-D = 21.5 Hz), 32.2, 30.8. FT-IR: ν (cm-1) 3439, 3027, 2921,
2862, 2252, 1602, 1451, 1332, 1217. HRMS [ESI] calcd for C18H18DNNaO2 [M+Na]+ 305.1371,
found 305.1359.

9: yellow oil, (1.5 mmol, 0.41 g, 99%). 1H NMR (400 MHz, CDCl3) δ
7.53-7.49 (m, 2H), 7.43-7.32 (m, 3H), 2.07-1.97 (m, 1H), 1.96-1.86 (m,
1H), 1.58-1.47 (m, 1H), 1.45-1.34 (m, 1H), 1.24-1.14 (m, 1H), 0.87 (d, J =
6.8 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H), 0.13 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 141.2, 128.6, 128.5, 125.1, 120.9, 75.8, 44.1, 33.1, 27.8, 22.5, 22.4, 1.0. FT-IR: ν (cm-1)
3063, 3034, 2957, 2929, 2871, 2146, 1602, 1468, 1386, 1304, 1253.

5. Characterization of products

2a: white solid, (0.3 mmol, 49 mg, 82%), m.p. 46-47 oC. 1H NMR (400
MHz, CDCl3) δ 8.01-7.96 (m, 2H), 7.61-7.55 (m, 1H), 7.51-7.45 (m,
2H), 3.23-3.16 (m, 2H), 2.04-1.98 (m, 2H), 1.41 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 197.9, 136.0, 132.9, 128.2, 127.6, 124.1, 34.3, 34.1,
31.5, 26.2. FT-IR: ν (cm-1) 2954, 2916, 2849, 2232, 1681, 1579, 1449, 1369, 1244. HRMS [ESI]
calcd for C13H15NNaO [M+Na]+ 224.1046, found 224.1039.

2b: pink solid, (0.3 mmol, 71 mg, 86%), m.p. 140-141 oC. 1H
NMR (400 MHz, CDCl3) δ 8.08-8.03 (m, 2H), 7.72-7.68 (m, 2H),
7.65-7.61 (m, 2H), 7.51-7.44 (m, 2H), 7.43-7.38 (m, 1H),
3.26-3.20 (m, 2H), 2.07-2.01 (m, 2H), 1.43 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 197.5, 145.6, 139.3, 134.7, 128.5, 128.2, 127.9, 126.9, 126.8, 124.2, 34.4, 34.2,
31.6, 26.3. FT-IR: ν (cm-1) 2933, 2875, 2855, 2236, 1677, 1604, 1474, 1373, 1240. HRMS [ESI]
calcd for C19H19NNaO [M+Na]+ 300.1359, found 300.1370.

2c: white solid, (0.3 mmol, 57 mg, 82%), m.p. 55-56 oC. 1H NMR
(400 MHz, CDCl3) δ 7.99-7.93 (m, 2H), 6.96-6.91 (m, 2H), 3.87
(s, 3H), 3.16-3.10 (m, 2H), 2.02-1.96 (m, 2H), 1.40 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 196.4, 163.2, 129.9, 129.1, 124.2,
113.4, 55.0, 34.5, 33.7, 31.6, 26.2. FT-IR: ν (cm-1) 2977, 2935, 2853, 2233, 1664, 1603, 1509,
1440, 1365, 1254. HRMS [ESI] calcd for C14H17NNaO2 [M+Na]+ 254.1151, found 254.1152.

2d: yellow solid, (0.3 mmol, 49 mg, 76%), m.p. 44-45 oC. 1H NMR
(400 MHz, CDCl3) δ 7.90-7.85 (m, 2H), 7.30-7.24 (m, 2H),
3.19-3.13 (m, 2H), 2.41 (s, 3H), 2.03-1.96 (m, 2H), 1.40 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 198.1, 144.2, 134.0, 129.4, 128.2, 124.7,
34.9, 34.5, 32.1, 26.7, 21.7. FT-IR: ν (cm-1) 2957, 2926, 2855, 2229, 1676, 1608, 1419, 1373,
1243. HRMS [ESI] calcd for C14H17NNaO [M+Na]+ 238.1202, found 238.1213.

2e: white solid, (0.3 mmol, 71 mg, 83%), m.p. 63-64 oC. 1H
NMR (400 MHz, CDCl3) δ 8.06-8.01 (m, 2H), 7.33-7.27 (m,
2H), 3.20-3.15 (m, 2H), 2.03-1.97 (m, 2H), 1.41 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 196.8, 152.8 (q, JC-F = 1.6 Hz),
134.7, 130.1, 124.5, 120.5, 120.3 (q, JC-F = 257.3 Hz), 34.7, 34.6, 32.0, 26.7. 19F NMR (376 MHz,
CDCl3) δ -57.6 (s). FT-IR: ν (cm-1) 2978, 2929, 2855, 2237, 1684, 1590, 1463, 1393, 1242. HRMS
[ESI] calcd for C14H14F3NNaO2 [M+Na]+ 308.0869, found 308.0862.
 2f: white solid, (0.3 mmol, 68 mg, 84%), m.p. 58-59 oC. 1H NMR
(400 MHz, CDCl3) δ 8.11-8.06 (m, 2H), 7.77-7.72 (m, 2H),
3.25-3.18 (m, 2H), 2.05-1.99 (m, 2H), 1.42 (s, 6H); 13C NMR
(100 MHz, CDCl3) δ 197.3, 139.1, 134.7 (q, JC-F = 32.6 Hz),
128.4, 125.8 (q, JC-F = 3.7 Hz), 124.5, 123.5 (q, JC-F = 271 Hz), 34.9, 34.6, 32.0, 26.7. 19F NMR
(376 MHz, CDCl3) δ -63.2 (s). FT-IR: ν (cm-1) 2983, 2925, 2852, 2234, 1686, 1460, 1367, 1239.
HRMS [ESI] calcd for C14H14F3NNaO [M+Na]+ 292.0920, found 292.0929.

2g: white solid, (0.3 mmol, 50 mg, 74%), m.p. 120-121 oC. 1H
NMR (400 MHz, CDCl3) δ 8.09-8.05 (m, 2H), 7.81-7.77 (m, 2H),
3.23-3.17 (m, 2H), 2.04-1.99 (m, 2H), 1.42 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 196.5, 138.9, 132.2, 128.0, 123.9, 117.3, 116.2,
34.5, 34.1, 31.5, 26.2. FT-IR: ν (cm-1) 2960, 2923, 2853, 2230, 1695, 1502, 1443, 1370, 1239.
HRMS [ESI] calcd for C14H14N2NaO [M+Na]+ 249.0998, found 249.0996.

2h: white solid, (0.3 mmol, 49 mg, 75%), m.p. 49-50 oC. 1H NMR
(400 MHz, CDCl3) δ 8.04-7.98 (m, 2H), 7.18-7.11 (m, 2H),
3.19-3.13 (m, 2H), 2.02-1.96 (m, 2H), 1.40 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 196.7, 165.9 (d, JC-F = 253.7 Hz), 132.9 (d, JC-F =
3.0 Hz), 130.7 (d, JC-F = 9.3 Hz), 124.6, 115.8 (d, JC-F = 21.8 Hz), 34.8, 34.5, 32.0, 26.7. 19F NMR
(376 MHz, CDCl3) δ -104.7 (s). FT-IR: ν (cm-1) 2978, 2929, 2854, 2235, 1685, 1596, 1489, 1372,
1220. HRMS [ESI] calcd for C13H14FNNaO [M+Na]+ 242.0952, found 242.0965.

2i: white solid, (0.3 mmol, 53 mg, 76%), m.p. 79-80 oC. 1H NMR
(400 MHz, CDCl3) δ 7.94-7.89 (m, 2H), 7.46-7.42 (m, 2H),
3.19-3.12 (m, 2H), 2.02-1.96 (m, 2H), 1.40 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 196.6, 139.4, 134.3, 129.0, 128.6, 124.0, 34.2,
34.1, 31.5, 26.2. FT-IR: ν (cm-1) 3353, 2980, 2928, 2855, 2231, 1684, 1588, 1488, 1367, 1241.
HRMS [ESI] calcd for C13H14ClNNaO [M+Na]+ 258.0656, found 258.0662.

2j: white solid, (0.3 mmol, 58 mg, 70%), m.p. 82-83 oC. 1H NMR
(400 MHz, CDCl3) δ 7.86-7.82 (m, 2H), 7.64-7.59 (m, 2H),
3.18-3.12 (m, 2H), 2.03-1.96 (m, 2H), 1.41 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 196.8, 134.7, 131.6, 129.1, 128.1, 124.0, 34.2,
34.1, 31.5, 26.2. FT-IR: ν (cm ) 2978, 2927, 2854, 2232, 1682, 1584, 1452, 1366, 1242. HRMS
-1

[ESI] calcd for C13H14BrNNaO [M+Na]+ 302.0151, found 302.0153.

2k: yellow oil, (0.3 mmol, 52 mg, 80%), 1H NMR (400 MHz, CDCl3)
δ 7.79-7.75 (m, 2H), 7.41-7.33 (m, 2H), 3.20-3.14 (m, 2H), 2.42 (s,
3H), 2.03-1.97 (m, 2H), 1.41 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
198.6, 138.5, 136.5, 134.2, 128.6, 128.6, 125.3, 124.7, 34.8, 34.6,
32.0, 26.7, 21.4. FT-IR: ν (cm-1) 2959, 2930, 2868, 2231, 1674, 1603, 1522, 1458, 1364, 1245.
HRMS [ESI] calcd for C14H17NNaO [M+Na]+ 238.1202, found 238.1207.
 2l: yellow solid, (0.3 mmol, 61 mg, 86%), m.p. 81-82 oC. 1H NMR
(400 MHz, CDCl3) δ 7.96-7.93 (m, 1H), 7.88-7.83 (m, 1H),
7.57-7.53 (m, 1H), 7.45-7.40 (m, 1H), 3.19-3.14 (m, 2H),
2.03-1.98 (m, 2H), 1.41 (s, 6H); 13C NMR (101 MHz, CDCl3) δ
196.6, 137.5, 134.6, 132.8, 129.6, 127.7, 125.7, 124.0, 34.2, 34.1, 31.5, 26.2. FT-IR: ν (cm-1) 2954,
2926, 2854, 2233, 1686, 1571, 1508, 1457, 1363, 1241. HRMS [ESI] calcd for C13H14ClNNaO
[M+Na]+ 258.0656, found 258.0667.

2m: yellow oil, (0.3 mmol, 61 mg, 87%). 1H NMR (400 MHz, CDCl3) δ
7.50-7.46 (m, 1H), 7.44-7.36 (m, 2H), 7.35-7.30 (m, 1H), 3.18-3.12 (m,
2H), 2.02-1.97 (m, 2H), 1.39 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
201.0, 138.5, 131.5, 130.4, 130.2, 128.5, 126.6, 124.0, 38.4, 34.3, 31.4,
26.2. FT-IR: ν (cm ) 2978, 2934, 2876, 2234, 1699, 1541, 1458, 1371, 1267. HRMS [ESI] calcd
-1

for C13H14ClNNaO [M+Na]+ 258.0656, found 258.0669.

2n: yellow oil, (0.3 mmol, 76 mg, 91%). 1H NMR (400 MHz, CDCl3) δ
7.63-7.58 (m, 1H), 7.42-7.35 (m, 2H), 7.33-7.27 (m, 1H), 3.15-3.08 (m,
2H), 2.02-1.96 (m, 2H), 1.38 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
201.9, 140.8, 133.3, 131.4, 128.0, 127.1, 123.9, 118.2, 38.2, 34.2, 31.4,
26.2. FT-IR: ν (cm-1) 2977, 2932, 2876, 2234, 1701, 1587, 1468, 1429, 1370, 1264. HRMS [ESI]
calcd for C13H14BrNNaO [M+Na]+ 302.0151, found 302.0157.

2o: yellow solid, (0.3 mmol, 56 mg, 70%), m.p. 75-76 oC.
1H NMR (400 MHz, CDCl ) δ 7.99-7.94 (m, 2H),
3

7.04-6.99 (m, 2H), 4.72 (q, J = 2.4 Hz, 2H), 3.17-3.11 (m,
2H), 2.02-1.96 (m, 2H), 1.86 (t, J = 2.4 Hz, 3H), 1.40 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 196.5, 161.4, 129.8,
129.5, 124.2, 114.2, 84.1, 72.7, 56.1, 34.5, 33.8, 31.6, 26.2, 3.2. FT-IR: ν (cm-1) 2983, 2924, 2856,
2234, 1671, 1600, 1508, 1421, 1374, 1221. HRMS [ESI] calcd for C17H19NNaO2 [M+Na]+
292.1308, found 292.1303.

2p: yellow solid, (0.3 mmol, 63 mg, 82%), m.p. 65-66 oC. 1H
NMR (400 MHz, CDCl3) δ 7.98-7.94 (m, 2H), 6.98-6.93 (m,
2H), 6.11-6.00 (m, 1H), 5.47-5.39 (m, 1H), 5.35-5.30 (m, 1H),
4.63-4.59 (m, 2H), 3.17-3.11 (m, 2H), 2.02-1.96 (m, 2H), 1.41
(s, 6H); 13C NMR (100 MHz, CDCl3) δ 196.4, 162.2, 131.9,
129.8, 129.2, 124.2, 117.8, 114.1, 68.4, 34.5, 33.7, 31.6, 26.2. FT-IR: ν (cm-1) 2977, 2929, 2234,
1676, 1599, 1509, 1420, 1365, 1221. HRMS [ESI] calcd for C16H19NNaO2 [M+Na]+ 280.1308,
found 280.1306.

2q: yellow oil, (0.3 mmol, 41 mg, 66%). 1H NMR (400 MHz, CDCl3) δ
2.67-2.61 (m, 2H), 2.41-2.32 (m, 1H), 1.89-1.74 (m, 6H), 1.71-1.63 (m,
1H), 1.40-1.14 (m, 5H), 1.33 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
211.8, 124.1, 50.6, 36.0, 33.8, 31.4, 28.1, 26.2, 25.3, 25.1. FT-IR: ν
(cm-1) 2977, 2929, 2855, 2234, 1707, 1450, 1372, 1243. HRMS [ESI] calcd for C13H21NNaO
[M+Na]+ 230.1515, found 230.1517.

2r: yellow solid, (0.3 mmol, 49 mg, 68%), m.p. 55-56 oC. 1H NMR
(400 MHz, CDCl3) δ 8.00-7.95 (m, 2H), 7.60-7.54 (m, 1H), 7.50-7.44
(m, 2H), 3.24-3.17 (m, 2H), 2.05-1.97 (m, 4H), 1.80-1.71 (m, 3H),
1.70-1.56 (m, 2H), 1.35-1.26 (m, 2H), 1.24-1.14 (m, 1H); 13C NMR
(100 MHz, CDCl3) δ 198.2, 136.1, 132.9, 128.2, 127.6, 122.9, 38.2, 35.3, 33.7, 33.3, 24.8, 22.6.
FT-IR: ν (cm-1) 3413, 2922, 2851, 2245, 1492, 1449, 1376, 1272. HRMS [ESI] calcd for
C16H19NNaO [M+Na]+ 264.1359, found 264.1353.

2s: white solid, (0.3 mmol, 51 mg, 75%), m.p. 45-46 oC. 1H NMR (400
MHz, CDCl3) δ 7.99-7.95 (m, 2H), 7.61-7.55 (m, 1H), 7.50-7.44 (m, 2H),
3.19-3.11 (m, 2H), 3.05-2.97 (m, 1H), 2.38-2.27 (m, 1H), 2.06-1.99 (m,
1H), 1.85-1.76 (m, 1H), 1.75-1.57 (m, 4H), 1.53-1.44 (m, 1H), 1.43-1.31
(m, 1H); C NMR (100 MHz, CDCl3) δ 197.8, 136.3, 132.9, 128.2, 127.6, 120.2, 42.5, 33.9, 32.3,
13

28.6, 28.2, 24.9, 21.5. FT-IR: ν (cm-1) 2933, 2862, 2234, 1677, 1597, 1449, 1354, 1278. HRMS
[ESI] calcd for C15H17NNaO [M+Na]+ 250.1202, found 250.1214.

2t (5:1): yellow oil, (0.3 mmol, 18 mg, 30%). 1H NMR (400 MHz, CDCl3)
δ 7.99-7.94 (m, 2.34H, two isomers), 7.61-7.56 (m, 1.17H, two isomers),
7.51-7.45 (m, 2.34H, two isomers), 3.18-3.08 (m, 1.17H, two isomers),
3.06-2.94 (m, 1.17H, two isomers), 2.81-2.73 (m, 1H, one isomer),
2.58-2.54 (m, 0.17H, one isomer), 2.54-2.45 (m, 1H, one isomer), 2.43-2.37 (m, 0.17H, one
isomer), 1.36 (d, J = 7.2 Hz, 0.51H, one isomer), 1.33 (d, J = 7.2 Hz, 3H, one isomer), 1.14 (d, J =
6.8 Hz, 0.51H, one isomer), 1.13 (d, J = 6.8 Hz, 3H, one isomer); 13C NMR (100 MHz, CDCl3) δ
198.4 & 198.2 (two isomers), 136.8 & 136.7 (two isomers), 133.5 & 133.4 (two isomers), 128.7
(overlap, two isomers), 128.1 & 128.0 (two isomers), 121.9 & 118.4 (two isomers), 43.6 & 41.4
(two isomers), 32.4 & 32.2 (two isomers), 31.1 & 26.4 (two isomers), 21.3 & 18.3 (two isomers),
15.3 & 11.3 (two isomers). FT-IR: ν (cm-1) 2963, 2927, 2879, 2856, 2238, 1685, 1598, 1411, 1317,
1258. HRMS [ESI] calcd for C13H16NO [M+H]+ 202.1226, found 202.1229.

2u: yellow solid, (0.3 mmol, 25 mg, 33%), m.p. 40-41 oC. 1H NMR
(400 MHz, CDCl3) δ 7.96-7.92 (m, 2H), 7.61-7.56 (m, 1H),
7.50-7.45 (m, 2H), 7.43-7.37 (m, 4H), 7.37-7.32 (m, 1H), 4.07 (dd, J
= 8.8, 6.0 Hz, 1H), 3.29-3.08 (m, 2H), 2.45-2.26 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 197.8, 136.0, 134.9, 133.0, 128.7, 128.3, 127.8, 127.5, 126.8, 120.1, 35.9,
34.6, 29.5. FT-IR: ν (cm-1) 3063, 2925, 2853, 2241, 1682, 1597, 1411, 1307, 1229. HRMS [ESI]
calcd for C17H15NNaO [M+Na]+ 272.1046, found 272.1032.

2v: yellow solid, (0.3 mmol, 24 mg, 30%), m.p. 59-60 oC. 1H
NMR (400 MHz, CDCl3) δ 7.96-7.91 (m, 2H), 7.61-7.55 (m, 1H),
7.50-7.44 (m, 2H), 7.29-7.25 (m, 2H), 7.22-7.17 (m, 2H), 4.02
(dd, J = 8.4, 6.4 Hz, 1H), 3.27-3.06 (m, 2H), 2.41-2.25 (m, 2H),
2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 198.3, 138.1, 136.5, 133.5, 132.3, 129.8, 128.7, 128.0,
127.2, 120.7, 36.0, 35.1, 30.0, 21.1. FT-IR: ν (cm-1) 2922, 2852, 2236, 1677, 1596, 1511, 1447,
1373, 1259. HRMS [ESI] calcd for C18H17NNaO [M+Na]+ 286.1202, found 286.1213.

2w: yellow solid, (0.3 mmol, 36 mg, 36%), m.p. 32-33 oC.
1H NMR (400 MHz, CDCl ) δ 7.97-7.92 (m, 2H), 7.63-7.56
3

(m, 1H), 7.51-7.42 (m, 4H), 7.28-7.23 (m, 2H), 4.11 (dd, J =
9.2, 5.6 Hz, 1H), 3.33-3.10 (m, 2H), 2.45-2.24 (m, 2H); 13C
NMR (100 MHz, CDCl3) δ 197.6, 148.6 (q, JC-F = 1.8 Hz), 135.8, 133.7, 133.1, 128.3, 128.3,
127.5, 121.2, 119.9 (q, JC-F = 256.3 Hz), 119.6, 35.3, 34.5, 29.6. 19F NMR (376 MHz, CDCl3) δ
-57.9 (s). FT-IR: ν (cm-1) 3065, 2928, 2855, 2243, 1684, 1509, 1418, 1369, 1255. HRMS [ESI]
calcd for C18H14F3NNaO2 [M+Na]+ 356.0869, found 356.0872.

2x: white solid, (0.3 mmol, 55 mg, 91%), m.p. 40-41 oC. 1H NMR (400
MHz, CDCl3) δ 7.98-7.94 (m, 2H), 7.61-7.55 (m, 1H), 7.50-7.44 (m,
2H), 4.28 (t, J = 6.4 Hz, 1H), 3.49 (s, 3H), 3.31-3.12 (m, 2H), 2.37-2.22
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 197.7, 135.9, 133.0, 128.2,
127.5, 117.4, 69.0, 57.6, 32.6, 27.2. FT-IR: ν (cm-1) 2934, 2853, 2834, 2332, 1737, 1683, 1596,
1449, 1347, 1281. HRMS [ESI] calcd for C12H13NNaO2 [M+Na]+ 226.0838, found 226.0846.

2y: yellow oil, (0.3 mmol, 19 mg, 31%). 1H NMR (400 MHz, CDCl3) δ
7.98-7.94 (m, 2H), 7.61-7.56 (m, 1H), 7.50-7.45 (m, 2H), 4.33 (q, J =
6.8 Hz, 1H), 4.17-4.11 (m, 1H), 4.02-3.95 (m, 1H), 3.41-3.32 (m, 1H),
3.27-3.18 (m, 1H), 1.54 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 196.8, 136.2, 132.9, 128.2, 127.6, 118.4, 65.0, 64.5, 37.7, 19.3. FT-IR: ν (cm-1) 2994,
2925, 2883, 2255, 1683, 1597, 1581, 1449, 1341, 1269. HRMS [ESI] calcd for C12H13NNaO2
[M+Na]+ 226.0838, found 226.0844.

2z-a: yellow oil, (0.3 mmol, 17 mg, 27%). 1H NMR (400 MHz,
CDCl3) δ 7.99-7.95 (m, 2H), 7.61-7.58 (m, 1H), 7.50-7.45 (m, 2H),
3.30-3.15 (m, 2H), 2.78-2.69 (m, 1H), 2.18-2.08 (m, 1H), 1.99-1.89
(m, 1H), 1.72-1.55 (m, 3H), 1.55-1.43 (m, 1H), 1.00-0.94 (m, 3H);
13C NMR (100 MHz, CDCl ) δ 198.4, 136.5, 133.4, 128.7, 128.0, 122.0, 35.6, 34.5, 30.9, 26.4,
3

20.4, 13.6. FT-IR: ν (cm ) 2960, 2930, 2873, 2237, 1684, 1598, 1449, 1373, 1225. HRMS [ESI]
-1

calcd for C14H17NNaO [M+Na]+ 238.1202, found 238.1193.

2z-b: yellow oil, (0.3 mmol, 8 mg, 13%). 1H NMR (400 MHz,
CDCl3) δ 7.97-7.93 (m, 2H), 7.60-7.54 (m, 1H), 7.49-7.44 (m, 2H),
3.04 (t, J = 7.2 Hz, 2H), 2.57-2.49 (m, 1H), 2.04-1.85 (m, 2H),
1.73-1.63 (m, 4H), 1.09 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 199.2, 136.7, 133.2, 128.7, 128.0, 122.0, 37.6, 33.3, 31.4, 25.5, 21.7, 11.6. FT-IR: ν
(cm-1) 2924, 2852, 2237, 1685, 1598, 1449, 1362, 1260. HRMS [ESI] calcd for C14H17NNaO
[M+Na]+ 238.1202, found 238.1195.
 3-a: yellow oil, (0.3 mmol, 24 mg, 33%). 1H NMR (400 MHz,
CDCl3) δ 7.31-7.26 (m, 2H), 7.22-7.15 (m, 3H), 2.63 (t, J = 7.2
Hz, 2H), 2.60-2.55 (m, 2H), 2.46 (t, J = 7.2 Hz, 2H), 1.97-1.89
(m, 2H), 1.83-1.77 (m, 2H), 1.33 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 208.3, 140.9, 128.0, 128.0, 125.6, 124.0, 41.6, 38.1, 34.6, 33.7, 31.4, 26.1, 24.7. FT-IR:
ν (cm-1) 2956, 2930, 2870, 2241, 1712, 1495, 1412, 1339, 1265. HRMS [ESI] calcd for
C16H21NNaO [M+Na]+ 266.1515, found 266.1503.

3-b: yellow oil, (0.3 mmol, 15 mg, 21%). 1H NMR (400 MHz,
CDCl3) δ 7.41-7.31 (m, 5H), 3.95 (dd, J = 8.8, 6.0 Hz, 1H),
2.72-2.52 (m, 2H), 2.43-2.37 (m, 2H), 2.25-2.06 (m, 2H),
1.56-1.49 (m, 1H), 1.49-1.42 (m, 2H), 0.88 (d, J = 6.4 Hz, 6H);
13C NMR (100 MHz, CDCl ) δ 209.0, 134.8, 128.7, 127.8, 126.8, 120.0, 40.6, 38.5, 35.8, 32.1,
3

29.1, 27.2, 21.8, 21.8. FT-IR: ν (cm-1) 3027, 2977, 2934, 2234, 1713, 1454, 1371, 1291, 1243.
HRMS [ESI] calcd for C16H21NNaO [M+Na]+ 266.1515, found 266.1527.

4 (a:b = 4:1): yellow oil, (0.3 mmol, 32 mg, 55%). 1H NMR (400
MHz, CDCl3) δ 2.66-2.56 (m, 2.52H, two isomers), 2.46-2.38 (m,
2.52H, two isomers), 1.84-1.77 (m, 2H, one isomer), 1.65-1.53 (m,
2.52H, two isomers), 1.52-1.42 (m, 0.78H, one isomer), 1.36-1.32
(m, 0.26H, one isomer), 1.33 (s, 6H, one isomer), 1.32-1.20 (m, 4.52H, two isomers), 1.07 (t, J =
7.2 Hz, 0.78H, one isomer), 0.92-0.84 (m, 4.56H, two isomers); 13C NMR (100 MHz, CDCl3) δ
(major isomer a) 209.3, 124.5, 43.0, 38.5, 34.3, 31.9, 31.4, 26.6, 23.5, 22.4, 13.9; δ (minor
isomer b) 209.7, 121.7, 41.1, 39.5, 32.6, 27.7, 25.7, 25.6, 22.3, 22.3, 11.5. FT-IR: ν (cm-1) 2957,
2930, 2872, 2235, 1715, 1458, 1340, 1294. HRMS [ESI] calcd for C12H21NNaO [M+Na]+
218.1515, found 218.1505.

5-a: yellow oil, (0.3 mmol, 19 mg, 28%). 1H NMR (400 MHz,
CDCl3) δ 7.41-7.30 (m, 5H), 3.95 (dd, J = 8.8, 6.0 Hz, 1H),
2.71-2.62 (m, 1H), 2.60-2.50 (m, 1H), 2.43-2.38 (m, 2H),
2.25-1.16 (m, 1H), 2.15-2.06 (m, 1H), 1.58-1.51 (m, 2H),
1.35-1.28 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 209.4, 135.3, 129.2,
128.2, 127.2, 120.5, 42.7, 39.0, 36.2, 29.5, 25.9, 22.3, 13.8. FT-IR: ν (cm-1) 2958, 2929, 2871,
2241, 1712, 1495, 1412, 1374, 1258. HRMS [ESI] calcd for C15H19NNaO [M+Na]+ 252.1359,
found 252.1354.

5-b: yellow oil, (0.3 mmol, 10 mg, 14%). 1H NMR (400 MHz,
CDCl3) δ 7.31-7.26 (m, 2H), 7.22-7.14 (m, 3H), 2.75-2.67 (m,
1H), 2.67-2.56 (m, 4H), 2.44 (t, J = 7.2 Hz, 2H), 1.97-1.85 (m,
3H), 1.78-1.71 (m, 1H), 1.32 (d, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 208.9, 141.4, 128.5, 128.4, 126.0, 122.5, 42.1, 39.5, 35.0, 29.7, 27.7, 25.1, 24.9,
18.1. FT-IR: ν (cm-1) 2924, 2853, 2239, 1712, 1455, 1412, 1373, 1261. HRMS [ESI] calcd for
C15H19NNaO [M+Na]+ 252.1359, found 252.1356.
 6-a: yellow oil, (0.3 mmol, 26 mg, 51%). 1H NMR (400 MHz, CDCl3) δ
2.62-2.56 (m, 2H), 2.41 (t, J = 7.2 Hz, 2H), 1.83-1.78 (m, 2H),
1.65-1.55 (m, 2H), 1.32 (s, 6H), 0.90 (t, J = 7.6 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 208.7, 124.0, 44.4, 38.0, 33.7, 31.4, 26.1, 16.8, 13.2. FT-IR: ν (cm-1) 2960, 2926,
2854, 2235, 1716, 1489, 1373, 1261. HRMS [ESI] calcd for C10H17NNaO [M+Na]+ 190.1202,
found 190.1199.

8 (D/H = 2.33): yellow oil, (0.3 mmol, 37 mg, 44%). 1H NMR

(400 MHz, CDCl3) δ 7.93-7.89 (m, 2H), 7.65-7.59 (m, 1H),
7.53-7.47 (m, 2H), 7.34-7.28 (m, 2H), 7.25-7.21 (m, 3H),
5.10-5.04 (m, 1H), 4.88-4.82 (m, 1H), 4.45 (t, J = 6.4 Hz,
0.3H), 2.99-2.85 (m, 2H), 2.39-2.21 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 194.3 & 194.3 (two
isomers), 139.8 (overlap, two isomers), 134.3 (overlap, two isomers), 134.1 (overlap, two isomers),
128.9 (overlap, two isomers), 128.7 (overlap, two isomers), 128.5 (overlap, two isomers), 127.8
(overlap, two isomers), 126.5 (overlap, two isomers), 117.8 (overlap, two isomers), 71.7 & 71.6
(two isomers), 68.4 & 68.3 (two isomers), 35.0 & 34.9 (two isomers), 30.8 & 30.8 (two isomers).
FT-IR: ν (cm-1) 3063, 3028, 2926, 2855, 1699, 1598, 1497, 1450, 1367, 1287. HRMS [ESI] calcd
for C18H17NNaO2 [M+Na]+ 302.1151, found 302.1139. HRMS [ESI] calcd for C18H16DNNaO2
[M+Na]+ 303.1214, found 303.1213.

10: yellow oil, (0.2 mmol, 24 mg, 56%). 1H NMR (400 MHz, CDCl3)
δ 7.41-7.36 (m, 2H), 7.26-7.21 (m, 1H), 7.11-7.07 (m, 2H), 2.82-2.76
(m, 2H), 2.04-1.99 (m, 2H), 1.42 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 170.4, 150.0, 129.0, 125.5, 120.9, 35.1, 31.5, 30.1, 26.0.
FT-IR: ν (cm ) 3065, 2980, 2932, 2877, 2235, 1758, 1692, 1593, 1493, 1373, 1297. HRMS [ESI]
-1

calcd for C13H15NNaO2 [M+Na]+ 240.0995, found 240.0965.

11: white solid, (0.2 mmol, 29 mg, 86%), m.p. 132-133 oC.. 1H
NMR (400 MHz, CDCl3) δ 7.97-7.92 (m, 2H), 7.57-7.51 (m, 1H),
7.47-7.41 (m, 2H), 5.82 (d, J = 16 Hz, 2H), 3.03-2.96 (m, 2H),
2.00-1.93 (m, 2H), 1.25 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
200.0, 180.0, 136.7, 133.1, 128.6, 128.1, 41.6, 35.1, 34.4, 25.7. FT-IR: ν (cm-1) 3426, 3162, 2960,
2913, 2853, 2294, 1663, 1579, 1449, 1364, 1221. HRMS [ESI] calcd for C13H17NNaO2 [M+Na]+
242.1151, found 242.1153.

12: yellow solid, (0.1 mmol, 18 mg, 89%), m.p. 102-103 oC. 1H NMR (400
MHz, CDCl3) δ 7.43-7.32 (m, 5H), 7.16 (br, 1H), 5.39 (ddd, J = 6.4, 4.4,
1.6 Hz, 1H), 2.34 (d, J = 4.8 Hz, 2H), 1.23 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 177.2, 136.3, 135.0, 128.9, 128.6, 124.7, 101.7, 36.8, 36.0, 24.5.
FT-IR: ν (cm ) 3442, 2961, 2924, 2853, 2294, 1666, 1578, 1461, 1357, 1263. HRMS [ESI] calcd
-1

for C13H15NNaO [M+Na]+ 224.1046, found 224.1040.

 13: white solid, (0.5 mmol, 132 mg, 73%), m.p. 124-125 oC. 1H
NMR (400 MHz, CDCl3) δ 7.75-7.71 (m, 2H), 7.37-7.24 (m, 7H),
4.94 (t, J = 6.8 Hz, 1H), 4.58 (t, J = 6.0 Hz, 1H), 2.64 (d, J = 6.8
Hz, 2H), 2.42 (s, 3H), 2.29 (br, 1H), 1.65-1.55 (m, 2H), 1.50-1.40
(m, 1H), 1.23-1.12 (m, 1H), 0.84 (s, 3H), 0.81 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 144.7,
143.3, 137.0, 129.7, 128.5, 127.6, 127.1, 125.8, 74.8, 52.3, 34.8, 33.6, 33.2, 25.3, 24.9, 21.5.
FT-IR: ν (cm-1) 3453, 3176, 2980, 2959, 2883, 1462, 1366, 1307, 1280. HRMS [ESI] calcd for
C20H27NNaO3S [M+Na]+ 384.1604, found 384.1611.

14: yellow oil, (0.2 mmol, 42 mg, 60%). 1H NMR (400 MHz, CDCl3) δ
7.67-7.63 (m, 2H), 7.25-7.13 (m, 7H), 5.25-5.21 (m, 1H), 3.41 (d, J = 13.2 Hz,
1H), 2.86 (d, J = 13.2 Hz, 1H), 2.40 (s, 3H), 2.13-2.05 (m, 2H), 1.27-1.20 (m,
2H), 0.80 (s, 3H), 0.79 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 142.3, 138.4,
138.1, 128.9, 127.9, 126.5, 126.4, 126.2, 54.9, 52.0, 32.0, 29.8, 28.1, 25.2, 23.6, 21.0. FT-IR: ν
(cm-1) 3088, 3030, 2952, 2864, 1599, 1495, 1455, 1334, 1268. HRMS [ESI] calcd for
C20H25NNaO2S [M+Na]+ 366.1498, found 366.1493.

15: white solid, (0.1 mmol, 19 mg, 87%), m.p. 123-124 oC. 1H NMR
(400 MHz, CDCl3) δ 7.98-7.94 (m, 2H), 7.58-7.52 (m, 1H),
7.48-7.42 (m, 2H), 3.05-2.98 (m, 2H), 2.05-1.99 (m, 2H), 1.29 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 199.7, 183.9, 136.8, 133.1,
128.6, 128.1, 41.6, 34.4, 34.3, 25.1. FT-IR: ν (cm-1) 3062, 2979, 2922, 2852, 1678, 1583, 1450,
1408, 1289. HRMS [ESI] calcd for C13H15O3 [M-H]- 219.1027, found 219.1057.
6. 1H, 13C, and 19F NMR spectra
7. Mechanistic studies
a. Control Experiments

entry blue Leds Ir-F001 K2S2O8 Yield

1 none none 2.2 equiv. 38%

2 14w 6 mol% none N.D.

3 none 3 mol% 2.2 equiv. 38%

b. Emission Quenching Experiments (Stern-Volmer Studies):

Emission intensities were recorded using a FLS980 (Edinburgh Instrument, UK)

luminescence spectrophotometer. All Ir[dF(CF3)ppy]2(dtbbpy)PF6 solutions were
excited at 350 nm and the emission intensity was collected at 475 nm. In a typical
experiment, to a 3·10-6 M solution of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.04 M solution
of Bu4NCl in PhCF3/H2O (10:1) was added the appropriate amount of a quencher in a
screw-top quartz cuvette. After degassing the sample with a stream of N2 for 10
minutes, the emission of the sample was collected.

K2S2O8
1.7

1.6

1.5

1.4
I0/I

1.3

1.2

1.1

1.0

0.9
0.000 0.002 0.004 0.006 0.008 0.010
Quencher concentration [M]
 250000

200000

150000

Intensity/a.u.
100000

50000

350 400 450 500 550 600 650 700

Wavelength/nm

c. Measurement of quantum yield

A cuvette was charged with 1a (0.3 mmol, 1.0 equiv.), K2S2O8 (0.66 mmol, 2.2
equiv.), Ir{[dF(CF3)-ppy]2(dtbbpy)}(PF6)(0.009 mmol, 0.03 equiv.), Bu4NCl (0.12
mmol, 0.04equiv.), and 3.3 mL PhCF3/H2O. The sample was irradiated (λ=450 nm,
slit width = 3.0 mm, slit height 5.0 mm with intensity of 1.499 mW·cm-2) for 2253 s
(37 min 33 s). After irradiation, the yield of product formed was determined by 1H
NMR based on a 1,3,5-trimethoxybenzene standard. The quantum yield was
determined as follows.
ϕ = Mole number for product/Mole number for absorption of photons = 4.7

n2a: the mole number of the product 2a; t: reaction time (2253 s, 37 min 33 s); NA:
6.02×1023/mol; f: 1-10-A (450 nm, A=1.26); P: P=E*S (E: illumination intensity,
E=1.499 mW/cm2; S: the area that irradiated S= 0.15 cm2); λ: wavelength (λ=
4.50×10-7 m); h: planck constant (h=6.626×10-34 J*s); c: velocity of light (c=3×108
m/s).
 d. Cyclic Voltammograms of 1a

All voltammograms were taken at room temperature using a saturated calomel

(SCE) reference electrode, a mesh platinum (Pt) counter electrode, and a glassy
carbon working electrode. The conditions of the experiments were the following: an
acetonitrile solution of 100 mM tetrabutylammonium hexafluorophosphate (NBu4PF6)
and 1 mM aryl alcohol, a scan rate of 0.1 V/s, and a positive initial scan direction. The
reported potentials were averages over segments, and were taken at half-height of the
cathodic peaks (Ep/2) of 1a, since all oxidations were nonreversible. To convert the
potentials from SCE to Fc/Fc+ reference, 380 mV were subtracted from the measured
values. The positive peaks on the return sweep of most substrates were thought to
signify an ECE-type mechanism.

0.00035

0.00030
Current (A)

0.00025

0.00020

Ep/2=2.5vs. SCE
0.00015

0.00010

0.00005

0.00000

-0.00005
0.0 0.5 1.0 1.5 2.0 2.5 3.0

Potential (V. vs. SCE)