ACCEPTED MANUSCRIPT
1
Compound 2: H-NMR (CDCl , 600 MHz, ppm), δ 7.58-7.53 (m, 3 H), 7.20 (d, J =
3
2
3
4.60 Hz, 1 H), 6.95 (s, 2 H ), 6.90 (d, J = 13.20 Hz, 2 H), 6.58 (s, 1 H), 5.98 (s, 1 H),
.84 (s, 3 H), 2.60 (s, 3 H), 2.34 (s, 3 H), 2.11 (s, 6 H), 1.43 (s, 3 H), 1.40 (s, 3 H)
1
3
(
Figure S12). C NMR (150 MHz, CDCl ) δ 160.38, 154.51, 153.09, 141.79, 141.56,
3
1
1
39.94, 138.57, 135.77, 135.19, 132.00, 131.25, 130.87, 129.50, 128.97, 120.73, 117.17,
+
17.07, 114.25, 55.38, 21.22, 19.59, 14.76, 13.65, 13.43(Figure S16). HRMS (ESI ):
+
m/z calcd for C H BF N O [M] : 484.24980; found: 484.25009(Figure S21).
30
31
2
2
1
Compound 3: H-NMR (CDCl , 600 MHz, ppm), δ 7.64-7.57 (m, 6 H), 7.21 (d, J =
3
1
6.20 Hz, 2 H), 6.94 (m, 6.92-6.96, 6 H), 6.61 (s, 2 H), 3.85 (s, 6 H), 2.35 (s, 3 H), 2.12
1
3
(
s, 6 H), 1.44 (s, 6 H) (Figure S13). C NMR (150 MHz, CDCl ) δ 160.35, 152.54,
3
1
1
41.07, 138.57, 137.98, 135.50, 132.37, 131.36, 129.68, 128.99, 128.90, 117.40,
+
17.14, 114.28, 55.40, 21.24, 19.63, 13.65(Figure S17). HRMS (ESI ): m/z calcd for
+
C H BF N O [M] : 602.29161; found: 602.29016 (Figure S22).
38
37
2
2
2
4
.2.3. Compound 4-5. In a round bottom flask equipped with a dean stark apparatus, p-
methoxybenzaldehyde (218 mg, 1.6 mmol), piperidine (1 mL) and a crystal of p-TsOH
were added to a stirred solution of compound 1 (147.0 mg, 0.40 mmol) in toluene (20
mL). The mixture was heated to reflux and reaction was monitored by TLC 1:1 CH Cl
2
2
:
Hexanes. When the starting material had been consumed, the mixture was cooled to
room temperature and solvent was evaporated under reduced pressure. Water (100 mL)
added to the residues and the product was extracted with the chloroform (3 x 100 mL).
The combined organic phase was dried over Na SO and the organic solvent was
2
4
evaporated under reduced pressure. The resulting crude residue was purified by silica
gel column chromatography, eluted with CH Cl /petroleum ether = 1:1, then 3:1, then
2
2
pure CH Cl , affording the desired compound 4 (41 mg, 14%) and compound 5 (7 mg,
2
2
1
2
6
%) as black powder. Compound 4 H-NMR (CDCl , 400 MHz, ppm), δ 7.67-7.60 (m,
3
H), 7.05 (s, 2 H), 7.01-6.76 (m, 12 H), 6.66 (s, 1 H), 5.63 (d, J = 12.80 Hz, 1 H), 3.87
1
3
(
s, 6 H), 3.81 (s, 3 H), 2.46 (s, 3 H), 2.13 (s, 6 H), 1.52 (s, 3 H) (Figure S14). C NMR
(
150 MHz, CDCl ) δ 160.56, 160.26, 159.42, 153.68, 152.20, 141.80, 141.11, 138.91,
3
1
1
5
37.31, 136.61, 135.03, 133.32, 131.93, 131.55, 131.21, 130.19, 129.76, 129.54,
29.19, 128.96, 128.93, 127.92, 118.30, 117.78, 117.50,117.28, 114.33, 114.27, 113.98,
+
5.41, 55.34, 30.32, 29.71, 29.68, 21.20, 19.74, 14.01. (Figure S18). HRMS (ESI ): m/z
+
calcd for C H BF N O [M] : 720.33350; found: 720.33136 (M+)(Figure S23).
4
6
43
2
2
3
1
8