11
(ddd, J = 12.2, 6.7, 5.3 Hz, 1H), 3.14 (dd, J = 13.9, 5.8 Hz, 1H), 3.04 (dd, J = 13.9, 6.8 Hz, 1H), 2.86 (td, J = 6.1, 3.1 Hz, 2H), 1.75 –
1.58 (m, 2H), 1.58 – 1.44 (m, 1H), 0.91 (dd, J = 6.3, 4.0 Hz, 6H). 13C NMR (101 MHz, CDCl3) ꢃ 173.0, 171.8, 157.0, 135.9, 135.0,
133.2, 129.2, 128.4, 128.4, 127.0, 126.8, 126.5, 126.4, 53.2, 52.6, 52.3, 45.4, 41.3, 41.3, 38.0, 29.0, 24.8, 22.9, 22.3.
Methyl (1,2,3,4-tetrahydroisoquinoline-2-carbonyl)-L-leucinate (6s)
1
Using the same procedure as 6b, colorless oil, 88% yield. H NMR (400 MHz, CDCl3) ꢃ 7.21 – 7.07 (m, 4H), 5.14 (d, J = 8.0 Hz,
1H), 4.58 (t, J = 7.8 Hz, 1H), 4.55 (s, 2H), 3.73 (s, 3H), 3.67 (dt, J = 11.5, 5.6 Hz, 1H), 3.55 (dt, J = 12.0, 5.8 Hz, 1H), 2.84 (q, J = 6.2
Hz, 2H), 1.74 (dp, J = 13.3, 6.6 Hz, 1H), 1.67 – 1.50 (m, 2H), 0.96 (s, 3H), 0.94 (s, 3H). 13C NMR (101 MHz, CDCl3) ꢃ 175.3, 157.1,
135.0, 133.3, 128.3, 126.6, 126.4, 52.2, 52.2, 45.4, 41.8, 41.2, 29.0, 24.9, 22.9, 22.0.
Methyl (S)-2-((S)-4-methyl-2-(1,2,3,4-tetrahydroisoquinoline-2-carboxamido) pentanamido)-3-(naphthalen-2-yl) propanoate (9s)
1
Using the same procedure as 6a, colorless oil, 72% yield. H NMR (400 MHz, CDCl3) ꢃ 7.76 – 7.63 (m, 3H), 7.59 (s, 1H), 7.41 –
7.33 (m, 2H), 7.26 – 7.22 (m, 1H), 7.19 (dt, J = 7.3, 3.7 Hz, 2H), 7.16 – 7.11 (m, 1H), 7.08 (dd, J = 5.3, 3.6 Hz, 1H), 6.99 (d, J = 7.8
Hz, 1H), 4.92 (q, J = 6.9 Hz, 1H), 4.82 (d, J = 8.0 Hz, 1H), 4.46 – 4.36 (m, 3H), 3.50 (dt, J = 11.8, 5.8 Hz, 1H), 3.41 (dt, J = 12.1, 5.9
Hz, 1H), 3.32 (dd, J = 13.9, 5.7 Hz, 1H), 3.19 (dd, J = 13.9, 6.9 Hz, 1H), 2.77 (t, J = 5.4 Hz, 2H), 1.72 – 1.60 (m, 2H), 1.50 (q, J = 8.7,
8.2 Hz, 1H), 0.89 (t, J = 5.8 Hz, 6H). 13C NMR (101 MHz, CDCl3) ꢃ 173.1, 171.9, 157.0, 135.0, 133.5, 133.4, 133.2, 132.4, 128.4,
128.1, 128.0, 127.6, 127.6, 127.3, 126.7, 126.4, 126.4, 126.0, 125.6, 53.2, 52.7, 52.4, 45.3, 41.2, 41.2, 38.1, 29.0, 24.9, 22.9, 22.2.
Methyl (benzyl (methyl) carbamoyl)-L-leucinate (6t)
Using the same procedure as 6b, colorless oil, 70% yield. 1H NMR (400 MHz, CDCl3) ꢃ 7.32 (t, J = 7.5 Hz, 2H), 7.23 (d, J = 7.8 Hz,
3H), 5.03 (d, J = 8.0 Hz, 1H), 4.54 (q, J = 7.8 Hz, 1H), 4.48 (s, 2H), 3.70 (s, 3H), 2.88 (s, 3H), 1.71 – 1.44 (m, 3H), 0.92 (t, J = 5.7 Hz,
6H).13C NMR (101 MHz, CDCl3) ꢃ 175.0, 157.9, 137.7, 128.6, 127.3, 127.2, 52.3, 52.1, 52.1, 41.6, 34.2, 24.8, 22.9, 21.9.
Methyl (S)-2-((S)-2-(3-benzyl-3-methylureido)-4-methylpentanamido)-3-(naphthalen-2-yl) propanoate (9t)
1
Using the same procedure as 6a, colorless oil, 77% yield. H NMR (400 MHz, CDCl3) ꢃ 7.83 – 7.72 (m, 3H), 7.62 (s, 1H), 7.49 –
7.41 (m, 2H), 7.35 – 7.21 (m, 4H), 7.16 (d, J = 7.2 Hz, 2H), 4.94 (q, J = 6.6 Hz, 1H), 4.75 (d, J = 7.6 Hz, 1H), 4.46 – 4.36 (m, 2H), 4.26
(d, J = 16.0 Hz, 1H), 3.71 (s, 3H), 3.34 (dd, J = 13.9, 5.7 Hz, 1H), 3.23 (dd, J = 13.8, 6.7 Hz, 1H), 2.77 (s, 3H), 1.62 (dt, J = 12.9, 6.6
Hz, 1H), 1.53 (dt, J = 12.8, 6.5 Hz, 1H), 1.49 – 1.37 (m, 1H), 1.33 (dd, J = 19.5, 11.1 Hz, 1H), 0.87 (d, J = 6.2 Hz, 6H). 13C NMR (101
MHz, CDCl3) ꢃ 173.1, 171.9, 157.9, 137.6, 133.6, 133.4, 132.4, 128.7, 128.1, 127.7, 127.6, 127.4, 127.3, 127.1, 126.0, 125.8, 53.2,
52.9, 52.3, 52.1, 50.0, 38.0, 34.4, 24.7, 23.0, 22.0.
(+)-Pinanediol-N-(2-pyrazinecarbonyl)-L-leucine-L-(2-naphthyl)-alanine-L-proline boronate (8g)
Using the same procedure as 8a, colorless oil. 1H NMR (400 MHz, CDCl3) ꢃ 9.33 (s, 1H), 8.71 (d, J = 2.4 Hz, 1H), 8.44 (d, J = 1.4
Hz, 1H), 8.05 (d, J = 8.8 Hz, 1H), 7.75 – 7.59 (m, 4H), 7.43 (d, J = 8.3 Hz, 1H), 7.34 (dd, J = 9.1, 5.2 Hz, 2H), 7.02 (d, J = 8.0 Hz, 1H),
4.94 (dt, J = 13.7, 7.0 Hz, 1H), 4.66 (dd, J = 15.3, 7.7 Hz, 1H), 4.36 (d, J = 7.4 Hz, 1H), 3.52 – 3.39 (m, 1H), 3.29 – 3.00 (m, 3H), 2.54
(dd, J = 17.1, 8.8 Hz, 1H), 2.44 – 2.31 (m, 1H), 2.19 (dd, J = 10.9, 5.5 Hz, 1H), 2.08 (t, J = 5.3 Hz, 1H), 1.97 – 1.86 (m, 3H), 1.68 (dd, J
= 16.0, 10.9 Hz, 4H), 1.57 (ddd, J = 21.5, 10.6, 4.4 Hz, 1H), 1.47 (s, 3H), 1.42 – 1.35 (m, 1H), 1.29 (s, 3H), 1.25 (dd, J = 8.5, 4.7 Hz,
1H), 0.91 (t, J = 6.1 Hz, 6H), 0.87 (s, 3H). 13C NMR (101 MHz, CDCl3) ꢃ 170.9, 168.8, 162.8, 147.3, 144.4, 144.0, 142.6, 133.7, 133.3,
132.2, 128.5, 128.1, 127.8, 127.6, 127.4, 125.7, 125.4, 85.9, 77.8, 52.1, 51.7, 51.3, 46.4, 41.5, 39.6, 39.4, 38.2, 35.6, 28.7, 27.1, 27.0,
26.3, 24.8, 24.1, 23.1, 21.8.
(+)-Pinanediol-N-(2-pyrazinecarbonyl)-L-leucine-L-phenylalanine-L-proline boronate (8h)
Using the same procedure as 8a, colorless oil. 1H NMR (400 MHz, CDCl3) ꢃ 9.35 (d, J = 1.4 Hz, 1H), 8.70 (d, J = 2.4 Hz, 1H), 8.46
(dd, J = 2.4, 1.5 Hz, 1H), 8.11 (d, J = 8.7 Hz, 1H), 7.28 – 7.09 (m, 7H), 4.98 – 4.59 (m, 2H), 4.36 – 4.26 (m, 1H), 3.58 – 3.44 (m, 1H),
3.19 – 2.91 (m, 3H), 2.00 – 1.92 (m, 1H), 1.90 – 1.77 (m, 4H), 1.74 – 1.62 (m, 4H), 1.40 (s, 3H), 1.31 (d, J = 1.9 Hz, 1H), 1.26 (s, 3H),
1.02 – 0.92 (m, 2H), 0.95 – 0.87 (m, 6H), 0.84 (s, 3H). 13C NMR (101 MHz, CDCl3) ꢃ 171.2, 169.2, 162.9, 147.2, 144.4, 142.6, 136.0,
129.9, 128.2, 126.8, 126.7, 85.9, 77.8, 52.4, 51.8, 51.3, 46.6, 41.4, 39.5, 38.8, 38.2, 35.4, 28.6, 27.2, 27.1, 26.2, 24.8, 24.0, 23.1, 21.7.
(+)-Pinanediol-N-(2-pyrazinecarbonyl)-L-phenylalanine-L-phenylalanine-L-proline boronate (8i)
Using the same procedure as 8a, colorless oil. 1H NMR (400 MHz, CDCl3) ꢃ 9.34 (d, J = 1.3 Hz, 1H), 8.74 (d, J = 2.4 Hz, 1H), 8.51
(dd, J = 2.3, 1.5 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 7.26 – 7.08 (m, 10H), 6.76 (t, J = 14.5 Hz, 1H), 4.90 – 4.74 (m, 2H), 4.40 – 4.29 (m,
1H), 3.22 – 3.08 (m, 0H), 3.03 – 2.85 (m, 0H), 2.53 (dd, J = 17.6, 8.1 Hz, 1H), 2.43 – 2.30 (m, 1H), 2.20 (dd, J = 10.7, 6.1 Hz, 1H),
2.06 (dd, J = 10.2, 4.8 Hz, 1H), 1.98 – 1.91 (m, 2H), 1.79 (dt, J = 16.2, 8.1 Hz, 2H), 1.62 (ddd, J = 12.1, 11.1, 5.6 Hz, 1H), 1.44 (s, 3H),
1.30 (s, 3H), 0.87 (s, 3H). 13C NMR (101 MHz, CDCl3) ꢃ 169.5, 168.4, 162.7, 147.4, 144.4, 142.7, 136.2, 130.0, 129.5, 129.3, 128.5,
128.2, 127.0, 126.6, 85.9, 77.8, 54.3, 52.4, 51.3, 46.4, 39.2, 38.4, 38.2, 35.5, 28.6, 27.2, 27.1, 26.2, 24.1.
(+)-Pinanediol-N-(2-pyrazinecarbonyl)-L-phenylalanine-L-(2-naphthyl)-alanine-L-proline boronate (8j)
Using the same procedure as 8a, colorless oil. 1H NMR (400 MHz, CDCl3) ꢃ 9.31 (d, J = 1.3 Hz, 1H), 8.71 (d, J = 2.2 Hz, 1H), 8.44
(dd, J = 2.2, 1.5 Hz, 1H), 8.22 (d, J = 8.4 Hz, 1H), 7.74 (dd, J = 7.0, 4.9 Hz, 3H), 7.54 – 7.34 (m, 4H), 7.25 – 7.15 (m, 5H), 7.03 (d, J =
7.9 Hz, 1H), 4.99 – 4.80 (m, 2H), 3.41 (t, J = 6.9 Hz, 1H), 3.15 (ddt, J = 18.7, 15.6, 4.7 Hz, 5H), 2.55 (dd, J = 17.3, 8.6 Hz, 1H), 2.46 –