Procedure for the synthesis of homopropargyl alcohol
In a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 3-bromo-1-propyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF3COOH (25 mol%) and MeCN (2 mL) at room temperature under N2 atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.
Procedure for the synthesis of allenyl alchols
In a 10 mL Schlenk tube, a mixture of aldehyde (0.5 mmol), was added to a stirred solution of 1-bromo-2-pentyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), CF3COOH (25 mol%) and MeCN (2 mL) at room temperature under N2 atmosphere. After 24 hours, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.
1-phenylbut-3-yn-1-ol (3a)20:98% yield (71.6 mg), colourless oil. 1H NMR (400 MHz, CDCl3) δ 7.46-7.34 (m, 4H), 7.30 (ddd, J = 8.5, 3.6, 1.6 Hz, 1H), 4.88 (t, J = 5.4 Hz, 1H), 2.71-2.56 (m, 2H), 2.45 (s, 1H), 2.19-1.96 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 142.4, 128.5, 128.0, 125.8, 80.7, 72.3, 71.0, 29.5.
1-(4-chlorophenyl)but-3-yn-1-ol (3b)20: 96% yield (86.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.33-7.25 (m, 4H), 4.80 (t, J = 5.1 Hz, 1H), 2.81 (s, 1H), 2.58 (dd, J = 6.4, 2.5 Hz, 2H), 2.06 (dd, J = 3.4, 1.7 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 140.9, 133.7, 128.6, 127.2, 80.3, 71.6, 71.4, 29.4.
1-(p-tolyl)but-3-yn-1-ol (3c)20:91% yield (72.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.7 Hz, 2H), 7.14 (d, J = 7.7 Hz, 2H), 4.79 (s, 1H), 2.58 (dd, J = 11.1, 8.7 Hz, 3H), 2.33 (s, 3H), 2.03 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 139.6, 137.7, 129.2, 125.8, 80.9, 72.2, 70.9, 29.3, 21.2.
1-(4-fluorophenyl)but-3-yn-1-ol (3d)20: 97% yield (79.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.46-7.32 (m, 2H), 7.05 (t, J = 8.7 Hz, 2H), 4.86 (t, J = 5.5 Hz, 1H), 2.62 (dd, J = 6.3, 2.6 Hz, 2H), 2.49 (d, J = 2.5 Hz, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 162.4 (d, J = 245 Hz), 138.2 (d, J = 3 Hz), 127.5 d, J = 8 Hz), 115.4 (d, J = 21 Hz), 80.4, 71.7, 71.2, 29.6.
1-(4-methoxyphenyl)but-3-yn-1-ol (3e)20:89% yield (78.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.29 (d, J = 8.6 Hz, 2H), 6.95-6.80 (m, 2H), 4.80 (t, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.64-2.58 (m, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 159.3, 134.8, 127.1, 113.9, 80.9, 72.0, 70.9, 55.3, 29.3.
1-(4-isopropylphenyl)but-3-yn-1-ol (3f)20:89% yield (83.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.2 Hz, 2H), 4.82 (s, 1H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.06 (t, J = 2.6 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 148.7, 139.9, 126.6, 125.8, 81.0, 72.3, 70.9, 33.9, 29.3, 24.0.
1-(3-methoxyphenyl)but-3-yn-1-ol (3g)20:95% yield (83.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.27 (dd, J = 10.3, 5.9 Hz, 1H), 6.99-6.93 (m, 2H), 6.84 (ddd, J = 8.2, 2.5, 1.0 Hz, 1H), 4.85 (t, J = 6.3 Hz, 1H), 3.81 (s, 3H), 2.69-2.59 (m, 2H), 2.51 (s, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 159.7, 144.2, 129.6, 118.1, 113.5, 111.3, 80.7, 72.3, 71.0, 55.3, 29.4.
1-(m-tolyl)but-3-yn-1-ol (3h)20:83% yield (66.5 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.24 (t, J = 7.5 Hz, 1H), 7.21-7.14 (m, 2H), 7.10 (d, J = 7.4 Hz, 1H), 4.82 (t, J = 6.4 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.35 (s, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.5, 138.2, 128.8, 128.4, 126.4, 122.9, 80.9, 72.4, 70.9, 29.4, 21.5.
1-(2-chlorophenyl)but-3-yn-1-ol (3i)20:96% yield (86.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 7.7, 1.4 Hz, 1H), 7.36-7.26 (m, 2H), 7.26-7.20 (m, 1H), 5.28 (dd, J = 7.8, 4.0 Hz, 1H), 2.80 (ddd, J = 16.9, 3.9, 2.7 Hz, 1H), 2.69 (s, 1H), 2.54 (ddd, J = 16.9, 7.8, 2.6 Hz, 1H), 2.10 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 139.7, 131.7, 129.4, 129.0, 127.1, 127.1, 80.3, 71.2, 68.7, 27.7.
1-(2-fluorophenyl)but-3-yn-1-ol (3j)20:95% yield (79.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.52 (td, J = 7.5, 1.5 Hz, 1H), 7.26 (ddd, J = 7.1, 4.6, 1.9 Hz, 1H), 7.16 (td, J = 7.5, 0.8 Hz, 1H), 7.02 (ddd, J = 10.4, 8.2, 0.9 Hz, 1H), 5.18 (dd, J = 7.2, 4.9 Hz, 1H), 2.74 (ddd, J = 16.8, 4.7, 2.6 Hz, 1H), 2.62 (ddd, J = 16.8, 7.6, 2.6 Hz, 2H), 2.07 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 160.0 (d, J = 244 Hz), 129.5, 129.3 (d, J = 8 Hz), 127.2 (d, J = 4 Hz), 124.3 (d, J = 3 Hz), 115.3 (d, J = 22 Hz), 80.3, 71.1, 66.4 (d, J = 2 Hz), 28.2.
1-(4-propoxyphenyl)but-3-yn-1-ol (3k)20:85% yield (86.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.5 Hz, 2H), 6.88 (d, J = 8.5 Hz, 2H), 4.83 (t, J = 6.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 2H), 2.68-2.58 (m, 2H), 2.36 (s, 1H), 2.07 (d, J = 2.3 Hz, 1H), 1.80 (dd, J = 14.1, 7.0 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 158.9, 134.4, 127.0, 114.4, 80.9, 72.1, 70.8, 69.5, 29.4, 22.6, 10.5.
1-(2,4-dimethylphenyl)but-3-yn-1-ol (3l)20:85% yield (74.0 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 7.9 Hz, 1H), 7.03 (d, J = 7.7 Hz, 1H), 6.95 (s, 1H), 5.04 (t, J = 6.4 Hz, 1H), 2.62-2.54 (m, 2H), 2.45 (d, J = 4.8 Hz, 1H), 2.30 (s, 3H), 2.29 (s, 3H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 137.6, 137.4, 134.6, 131.3, 127.0, 125.1, 81.1, 70.7, 68.8, 28.3, 21.0, 19.0.
1-(2,5-difluorophenyl)but-3-yn-1-ol (3m)20:94% yield (85.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.26 (ddd, J = 8.8, 5.8, 3.0 Hz, 1H), 7.10-6.79 (m, 2H), 5.24-5.07 (m, 1H), 2.83-2.48 (m, 3H), 2.10 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 158.9 (dd, J = 241, 2 Hz), 155.3 (dd, J = 238, 3 Hz), 131.2 (dd, J = 16, 7 Hz), 116.3 (dd, J = 24, 8 Hz), 115.5 (dd, J = 24, 9 Hz), 113.9 (dd, J = 25, 4 Hz), 79.7, 71.6, 65.9, 28.2 (d, J = 1 Hz).
1-(2,3-difluorophenyl)but-3-yn-1-ol (3n)20:87% yield (79.2 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.33-7.23 (m, 1H), 7.18-7.01 (m, 2H), 5.19 (dd, J = 6.9, 5.2 Hz, 1H), 2.82 (s, 1H), 2.74 (ddd, J = 16.8, 4.8, 2.6 Hz, 1H), 2.63 (ddd, J = 16.8, 7.4, 2.5 Hz, 1H), 2.08 (t, J = 2.5 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 150.2 (dd, J = 246, 12 Hz), 147.6 (dd, J = 246, 13), 131.9 (d, J = 10 Hz), 124.2 (dd, J = 7, 5 Hz), 121.8 (t, J = 3 Hz), 116.5 (d, J = 2 Hz), 79.8, 71.4, 66. 0 (t, J = 2 Hz), 28.2.
1-(2,3-dimethylphenyl)but-3-yn-1-ol (3o)20:87% yield (75.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 7.4 Hz, 1H), 7.17-7.04 (m, 2H), 5.15 (dd, J = 7.6, 5.0 Hz, 1H), 2.61-2.51 (m, 2H), 2.28 (s, 3H), 2.22 (s, 3H), 2.07 (d, J = 2.4 Hz, 1H), 1.97 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 140.4, 137.0, 133.2, 129.4, 125.8, 122.9, 81.2, 70.7, 69.3, 28.3, 20.7, 14.7.
1-(2-methoxy-4-methylphenyl)but-3-yn-1-ol (3p)20:85% yield (80.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.6 Hz, 1H), 6.77 (d, J = 7.6 Hz, 1H), 6.68 (s, 1H), 5.09- 4.96 (m, 1H), 3.83 (d, J = 6.7 Hz, 3H), 2.98 (s, 1H), 2.67 (dddd, J = 24.2, 10.1, 6.3, 2.6 Hz, 2H), 2.34 (s, 3H), 2.03 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 156.2, 138.9, 127.4, 126.8, 121.2, 111.4, 81.5, 70.4, 68.9, 55.2, 27.5, 21.6.
1-(3-chloro-5-fluorophenyl)but-3-yn-1-ol (3q)20:95% yield (94.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.19 (s, 1H), 7.07-6.99 (m, 2H), 4.84 (t, J = 4.6 Hz, 1H), 2.65-2.61 (m, 1H), 2.59 (dd, J = 6.5, 3.0 Hz, 1H), 2.11 (t, J = 2.6 Hz, 1H), 1.68 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 163.7 (d, J = 248 Hz), 146.2 (d, J = 7 Hz), 135.1 (d, J = 10 Hz), 121.9 (d, J = 4 Hz), 115.6 (d, J = 25 Hz), 111.4 (d, J = 22 Hz), 79.6, 71.8, 71.2 (d, J = 2 Hz), 29.4.
1-(4-fluoro-3-methoxyphenyl)but-3-yn-1-ol (3r)20:88% yield (85.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.09-7.01 (m, 2H), 6.88 (ddd, J = 8.3, 4.3, 2.1 Hz, 1H), 4.83 (t, J = 6.3 Hz, 1H), 3.89 (d, J = 5.9 Hz, 3H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.55 (s, 1H), 2.09 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 151.914.7 (d, J = 244 Hz), 147.6 (d, J = 11 Hz), 138.8 (d, J = 3 Hz), 118.1 (d, J = 7 Hz), 115.8 (d, J = 19 Hz), 110.9 (d, J = 2 Hz), 80.4, 71.9, 71.3, 56.2, 29.6.
1-(4-fluoro-3-methylphenyl)but-3-yn-1-ol (3s)20: 88% yield (78.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.24-7.08 (m, 2H), 6.97 (t, J = 8.9 Hz, 1H), 4.81 (t, J = 6.3 Hz, 1H), 2.61 (dd, J = 6.3, 2.4 Hz, 2H), 2.45 (s, 1H), 2.27 (s, 3H), 2.08 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 160.9 (d, J = 243 Hz), 137.87, 128.9 (d, J = 2 Hz), 125.0, 124.7(d, J = 8 Hz), 114.9 (d, J = 22 Hz), 80.6, 71.8, 71.1, 29.5, 14.7(d, J = 4 Hz)
2-(benzo[d][1,3]dioxol-4-yl)but-3-yn-1-ol (3t)20: 85% yield (80.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 6.95-6.89 (m, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.78 (dd, J = 7.6, 1.0 Hz, 1H), 5.96 (dd, J = 9.2, 1.1 Hz, 2H), 4.98 (dd, J = 10.2, 6.3 Hz, 1H), 2.84-2.58 (m, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 147.4, 144.1, 124.1, 121.8, 119.3, 108.2, 101.0, 80.5, 70.9, 68.3, 27.6.
1-(thiophen-2-yl)but-3-yn-1-ol (3u)20:88% yield (66.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.32-7.22 (m, 1H), 6.99 (ddd, J = 11.1, 6.1, 2.5 Hz, 2H), 5.11 (d, J = 3.7 Hz, 1H), 2.79-2.68 (m, 3H), 2.11 (dd, J = 5.2, 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 146.2, 126.7, 125.0, 124.2, 80.1, 71.5, 68.5, 29.5.
1-(4-chloropyridin-2-yl)but-3-yn-1-ol (3v)20:93% yield (84.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.46 (d, J = 5.3 Hz, 1H), 7.49 (d, J = 1.7 Hz, 1H), 7.26 (dd, J = 5.4, 2.0 Hz, 1H), 4.88 (t, J = 6.0 Hz, 1H), 2.78-2.65 (m, 2H), 2.06 (t, J = 2.6 Hz, 1H), 1.25 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 162.0, 149.4, 144.9, 123.3, 121.2, 80.0, 71.3, 71.1, 28.2.
1-(pyridin-3-yl)but-3-yn-1-ol (3w)20:95% yield (69.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 2.0 Hz, 1H), 8.47 (dd, J = 4.8, 1.5 Hz, 1H), 7.79 (dt, J = 7.9, 1.8 Hz, 1H), 7.33-7.26 (m, 1H), 4.92 (t, J = 6.4 Hz, 1H), 2.70-2.65 (m, 2H), 2.08 (t, J = 2.6 Hz, 1H), 1.35 – 1.23 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 148.9, 147.6, 138.3, 133.9, 123.5, 79.9, 71.5, 70.0, 29.3.
1-(quinolin-2-yl)but-3-yn-1-ol (3x)20:93% yield (92.0 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.4, 1.4 Hz, 1H), 7.59-7.49 (m, 2H), 5.07 (t, J = 5.9 Hz, 1H), 2.80 (ddd, J = 5.9, 2.5, 1.7 Hz, 2H), 2.02 (t, J = 2.7 Hz, 1H), 1.25 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 160.0, 146.5, 137.0, 129.9, 128.9, 127.8, 127.7, 126.7, 118.5, 80.5, 71.0, 71.0, 28.3.
1-(naphthalen-2-yl)but-3-yn-1-ol (3y)20: 94% yield (92.5 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.87-7.70 (m, 4H), 7.56-7.36 (m, 3H), 4.98 (t, J = 6.3 Hz, 1H), 2.75 (s, 1H), 2.69 (dd, J = 6.4, 2.6 Hz, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 139.9, 133.2, 133.2, 128.4, 128.1, 127.8, 126.3, 126.1, 124.8, 123.8, 80.8, 72.5, 71.2, 29.4.
1-(naphthalen-1-yl)but-3-yn-1-ol (3z)20: 96% yield (94.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.2 Hz, 1H), 7.89-7.83 (m, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69 (d, J = 7.2 Hz, 1H), 7.54-7.44 (m, 3H), 5.63 (dd, J = 8.2, 4.2 Hz, 1H), 2.87 (ddd, J = 17.0, 4.2, 2.7 Hz, 1H), 2.73 (ddd, J = 17.0, 8.2, 2.6 Hz, 2H), 2.12 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 137.8, 133.8, 130.2, 129.1, 128.5, 126.3, 125.7, 125.4, 123.0, 122.8, 81.0, 71.3, 69.3, 28.7.
1-(4-isopropylphenyl)-2-methyl-3λ5-buta-2,3-dien-1-ol (5a)20:76% yield (76.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 5.07 (s, 1H), 4.96-4.85 (m, 2H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.18 (s, 1H), 1.58 (t, J = 3.0 Hz, 3H), 1.24 (d, J = 7.0 Hz, 6H).13C NMR (100 MHz, CDCl3) δ 204.6, 148.6, 139.2, 126.6, 126.5, 102.7, 77. 9, 74.5, 33.9, 24.0, 14.7.
2-methyl-1-(p-tolyl)-3λ5-buta-2,3-dien-1-ol (5b)20:83% yield (54.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 5.05 (s, 1H), 4.96-4.82 (m, 2H), 2.34 (s, 3H), 2.30 (s, 1H), 1.56 (t, J = 3.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 204.7, 138.9, 137.5, 129.1, 126. 6, 102.7, 77.8, 74.5, 21.2, 14.7.
1-(4-fluorophenyl)-2-methyl-3λ5-buta-2,3-dien-1-ol (5c)20: 73% yield (73 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.34 (dd, J = 8.4, 5.6 Hz, 2H), 7.03 (t, J = 8.7 Hz, 2H), 5.08 (s, 1H), 4.93-4.86 (m, 2H), 2.39 (s, 1H), 1.55 (t, J = 3.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 162.3(d, J = 244 Hz), 137.5 (d, J = 3 Hz), 128.3 (d, J = 8 Hz), 115.2 (d, J = 21 Hz), 102.6, 78.1, 77.4, 74.0, 14.5.
2-methyl-1-(thiophen-2-yl)-3λ5-buta-2,3-dien-1-ol (5d)20:76% yield (63.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.29-7.25 (m, 1H), 7.02 (d, J = 3.1 Hz, 1H), 6.99-6.95 (m, 1H), 5.35 (s, 1H), 4.99-4.86 (m, 2H), 2.34 (d, J = 4.4 Hz, 1H), 1.69 (t, J = 3.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 204.4, 146.1, 126.6, 125.2, 125.0, 102.6, 78.6, 70.7, 14.7.