C. Roche et al. / Tetrahedron 66 (2010) 8325e8334
8333
6.78 (s, 1H),6.80e6.95 (m, 3H), 7.01e7.57 (m, 11H), 7.73 (m, 2H), 7.88
4H), 2.30 (d, 3H, J¼5.1 Hz), 3.37 (s, 9H), 3.61 (m, 2H), 4.02 (m, 2H),
4.08e4.37 (m, 4H), 4.58 (m, 1H), 6.54 (m, 1H), 6.76e6.94 (m, 3H),
7.02e7.52 (m, 11H), 7.72 (m, 2H), 7.88 (d, 2H, J¼7.5 Hz). 13C (75 MHz,
(d, 2H, J¼7.5 Hz). 13C (75 MHz, acetone-d6):
¼172.3, 170.5, 159.7,
d
157.7, 145.0, 142.1, 138.7, 138.2, 133.5, 130.0, 129.3, 128.7, 128.1, 127.6,
126.2,121.0, 115.3, 78.1, 68.2, 67.6, 67.3, 53.5, 51.9, 48.0, 44.7, 41.2, 29.6,
25.5, 23.6, 23.3, 22.1, 21.3. HRMS (ESI): [Cþ] (C45H56N3O6) calcd
734.4169, found 734.4170.
acetone-d6):
d¼172.6, 171.5, 157.3, 159.8, 145.1, 142.1, 138.7, 138.2,
133.4, 130.0, 129.7, 128.7, 128.1, 127.5, 126.2, 120.9, 115.2, 78.2, 68.2,
67.3, 67.3, 61.2, 57.8, 53.5, 48.0, 38.2, 31.9, 29.6, 25.7, 23.6, 23.3, 21.3,
20.0, 18.5, 16.1, 11.9. HRMS (ESI): [Cþ] (C48H62N3O6) calcd 776.4638,
found 776.4633.
5.3.27. [Fmoc-Gly-Phe-O-MPPTMA][PF6] Fmoc-Gly-Phe-O-9. Following
general procedure G using [H-Phe-O-MPPTMA][PF6] and Fmoc-Gly-
OH, [Fmoc-Gly-Phe-O-MPPTMA][PF6] is obtained in 85% yield as
5.3.32. [Fmoc-Gly-Ala-Phe-O-MPPTMA][PF6]
Fmoc-Gly-Ala-Phe-O-
a yellow oil. 1H NMR (300 MHz, acetone-d6):
d¼1.61 (m, 2H), 1.85 (m,
9. Following general procedure H using [Fmoc-Ala-Phe-O-MPPTMA]
[PF6] and Fmoc-Gly-OH, [Fmoc-Gly-Ala-Phe-O-MPPTMA][PF6] is
obtained in 98% yield as a yellow oil. 1H NMR (300 MHz, acetone-d6):
2H), 2.04 (m, 2H), 2.30 (d, 3H, J¼4.4 Hz), 2.96e3.24 (m, 2H), 3.36 (s,
9H), 3.59 (m, 2H), 3.86 (m, 2H), 4.02 (m, 2H), 4.17e4.40 (m, 3H), 4.86
(m, 1H), 6.78 (s, 1H), 6.88 (m, 2H), 7.05e7.45 (m, 16H), 7.54 (m, 1H),
7.73 (d, 2H, J¼7.2 Hz), 7.88 (d, 2H, J¼7.4 Hz). 13C (75 MHz, acetone-d6):
d
¼1.24 (d, 3H, J¼6.9 Hz),1.58 (m, 2H),1.86 (m, 2H), 2.07 (m, 2H), 2.29
(m, 3H), 2.90e3.25 (m, 2H), 3.34 (s, 9H), 3.56 (m, 2H), 3.80e4.07 (m,
4H), 4.16e4.40 (m, 3H), 4.48 (m, 1H), 4.81 (m, 1H), 6.77 (s, 1H),
6.80e6.95 (m, 3H), 7.05e7.54 (m, 17H), 7.69 (m, 2H), 7.87 (d, 2H,
d
¼171.2, 170.1, 159.7, 157.6, 145.0, 142.1, 138.8, 138.2, 137.5, 133.4, 130.0,
129.8, 129.3, 129.2, 128.7, 128.1, 127.8, 127.6, 126.2, 120.9, 115.2, 78.3,
68.1, 67.5, 67.3, 54.7, 53.5, 48.0, 44.7, 38.1, 29.4, 23.6, 23.2, 21.2. HRMS
(ESI): [Cþ] (C48H54N3O6) calcd 768.4012, found 768.4012.
J¼7.4 Hz). 13C (75 MHz, acetone-d6):
¼172.3, 170.3, 169.3, 158.8,
d
157.0, 144.2, 141.2, 137.7, 137.3, 136.7, 132.5, 129.3, 129.1, 128.7, 128.6,
128.2,127.2,126.9,126.7,125.3,120.0,114.3, 77.5, 67.3, 66.7, 66.4, 54.1,
52.7, 48.7, 47.0, 44.3, 37.1, 28.4, 22.7, 22.3, 20.3, 17.6. HRMS (ESI): [Cþ]
(C51H59N4O7) calcd 839.4383, found 839.4378.
5.3.28. [Fmoc-Gly-Val-O-MPPTMA][PF6] Fmoc-Gly-Val-O-9. Following
general procedure G using [H-Val-O-MPPTMA][PF6] and Fmoc-Gly-
OH, [Fmoc-Gly-Val-O-MPPTMA][PF6] is obtained in 95% yield as
a yellow oil. 1H NMR (300 MHz, acetone-d6):
d¼0.86 (d, 3H,
5.3.33. [Fmoc-Leu-Ala-Phe-O-MPPTMA][PF6]
Fmoc-Leu-Ala-Phe-O-
J¼7.0 Hz), 0.90 (d, 3H, J¼6.8 Hz), 1.58 (m, 2H), 1.85 (m, 2H), 2.04 (m,
2H), 2.22 (m, 1H), 2.30 (s, 3H), 3.35 (s, 9H), 3.58 (m, 2H), 3.88e4.08
(m, 4H), 4.20e4.40 (m, 3H), 4.56 (m, 1H), 6.82 (s, 1H), 6.84e6.98 (m,
3H), 7.09e7.51 (m, 11H), 7.73 (m, 2H), 7.88 (d, 2H, J¼7.5 Hz). 13C
9. Following general procedure H using [Fmoc-Ala-Phe-O-MPPTMA]
[PF6] and Fmoc-Leu-OH, [Fmoc-Leu-Ala-Phe-O-MPPTMA][PF6] is
obtained in 98% yield as a yellow oil. 1H NMR (300 MHz, acetone-d6):
d
¼0.92 (d, 3H, J¼6.3 Hz), 0.94 (d, 3H, J¼6.4 Hz), 1.25 (d, J¼7.0, 3H),
(75 MHz, acetone-d6):
d
¼171.5, 170.6, 159.7, 157.7, 145.0, 142.1, 138.5,
1.50e2.08 (m, 9H), 2.30 (m, 3H), 2.90e3.23 (m, 2H), 3.34 (s, 9H), 3.58
(m, 2H), 4.01 (m, 2H), 4.12e4.50 (m, 5H), 4.81 (m, 1H), 6.67e6.77 (m,
2H), 6.88 (m, 2H), 7.02e7.60 (m, 17H), 7.70 (m, 2H), 7.87 (d, 2H,
138.3, 133.4, 130.0, 129.5, 128.7, 128.1, 127.6, 126.2, 121.0, 115.3, 78.2,
68.2, 67.6, 67.3, 58.6, 53.5, 48.0, 44.8, 31.6, 29.7, 23.6, 23.3, 21.3, 19.7,
18.3. HRMS (ESI): [Cþ] (C44H54N3O6) calcd 720.4013, found 720.4015.
J¼7.4 Hz).13C (75 MHz, acetone-d6):
¼172.3,172.1,170.2,158.8,156.5,
d
144.2, 141.2, 137.2, 137.9, 136.7, 132.5, 129.3, 129.0, 128.4, 128.2, 127.7,
126.9, 126.7, 126.3, 126.2, 120.0, 114.3, 77.4, 67.3, 66.4, 66.4, 53.9, 53.7,
52.7 (t, JCeN¼3.7 Hz), 48.7, 47.1, 41.1, 37.3, 28.5, 24.6, 22.7, 22.4, 21.1,
20.3, 17.7. HRMS (ESI): [Cþ] (C55H67N4O7) calcd 895.5009, found
895.5006.
5.3.29. [Fmoc-Ile-Leu-O-MPPTMA][PF6] Fmoc-Ile-Leu-O-9. Following
general procedure G using [H-Leu-O-MPPTMA][PF6] and Fmoc-Ile-
OH, [Fmoc-Ile-Leu-O-MPPTMA][PF6] is obtained in 78% yield as
a yellow oil. 1H NMR (300 MHz, acetone-d6):
d¼0.73e0.98 (m, 12H),
1.17 (m, 1H), 1.45e1.75 (m, 6H), 1.86 (m, 2H), 1.94e2.12 (m, 3H), 2.31
(m, 3H), 3.37 (s, 9H), 3.58 (m, 2H), 3.94e4.17 (m, 3H), 4.19e4.40 (m,
3H), 4.65 (m, 1H), 6.55 (m, 1H), 6.80 (s, 1H), 6.91 (m, 2H), 7.03e7.50
(m, 10H), 7.48 (m, 1H), 7.72 (m, 2H), 7.88 (d, 2H, J¼7.6 Hz). 13C
5.3.34. [Fmoc-Val-Gly-Phe-O-MPPTMA][PF6] Fmoc-Val-Gly-Phe-O-
9. Following general procedure
H using [Fmoc-Gly-Phe-O-
MPPTMA][PF6] and Fmoc-Val-OH, [Fmoc-Val-Gly-Phe-O-MPPTMA]
(75 MHz, acetone-d6):
d
¼172.6, 172.4, 159.7, 157.2, 145.1, 142.1, 138.7,
[PF6] is obtained in 83% yield as a yellow oil. 1H NMR (300 MHz,
138.2, 133.5, 130.0, 129.5, 128.7, 128.1, 127.8, 126.2, 121.0, 115.3, 78.2,
68.2, 67.3, 67.3, 60.5, 53.5, 51.9, 48.1, 41.3, 38.1, 29.7, 25.6, 25.5, 23.3,
23.3, 22.1, 21.4, 16.2, 11.7. HRMS (ESI): [Cþ] (C49H64N3O6) calcd
790.4795, found 790.4798.
acetone-d6):
d
¼0.99 (d, 6H, J¼6.7 Hz), 1.58 (m, 2H), 1.86 (m, 2H),
2.07 (m, 3H), 2.29 (m, 3H), 2.95e3.20 (m, 2H), 3.34 (s, 9H), 3.56 (m,
2H), 3.70e4.05 (m, 4H), 4.18e4.55 (m, 4H), 4.80 (m, 1H), 6.71e6.82
(m, 2H), 6.86 (m, 2H), 7.05e7.54 (m, 16H), 7.53e7.73 (m, 3H), 7.86
(d, J¼7.5, 2H). 13C (75 MHz, acetone-d6):
¼171.9, 170.3, 168.9, 158.8,
d
5.3.30. [Fmoc-Leu-Ala-O-MPPTMA][PF6] Fmoc-Leu-Ala-O-9. Following
general procedure G using [H-Ala-O-MPPTMA][PF6] and Fmoc-Ile-
OH, [Fmoc-Leu-Ala-O-MPPTMA][PF6] is obtained in 94% yield as
158.1, 144.1, 141.2, 137.7, 137.2, 136.7, 132.5, 129.3, 129.0, 128.6, 128.4,
127.8, 127.2, 126.9, 126.7, 125.3, 120.0, 114.3, 77.4, 67.2, 66.6, 66.4,
61.1, 54.1, 52.6, 47.1, 42.4, 37.4, 30.5, 28.5, 22.7, 22.4, 20.3, 18.9, 17.8.
HRMS (ESI): [Cþ] (C53H63N4O7) calcd 867.4696, found 867.4693.
a yellow oil. 1H NMR (300 MHz, acetone-d6):
d¼0.90 (d, 3H, J¼5.8 Hz),
0.92 (d, 3H, J¼6.1 Hz), 1.40 (dd, 3H, J1¼7.2 Hz, J2¼3.2 Hz), 1.50e1.67
(m, 6H), 1.74 (m, 1H), 1.85 (m, 2H), 2.30 (d, 3H, J¼4.5 Hz), 3.32 (s, 9H),
3.56 (m, 2H), 4.00 (m, 2H), 4.18e4.43 (m, 4H), 4.59 (m, 1H), 6.65 (m,
1H), 6.78 (s, 1H), 6.89 (dd, 2H, J1¼8.5 Hz, J2¼3.4 Hz), 7.11e7.50 (m,
10H), 7.63e7.74 (m, 3H), 7.86 (d, 2H, J¼8.0). 13C (75 MHz, acetone-d6):
5.3.35. [Fmoc-Val-Leu-Ala-O-MPPTMA][PF6]
Fmoc-Val-Leu-Ala-O-
9. Following general procedure using [Fmoc-Leu-Ala-O-
H
MPPTMA][PF6] and Fmoc-Val-OH, [Fmoc-Val-Leu-Ala-O-MPPTMA]
[PF6] is obtained in 91% yield as a yellow oil. 1H NMR (300 MHz,
d
¼171.4,171.3, 158.7, 156.2, 144.2, 141.2, 137.9,137.2, 132.7, 129.0, 128.3,
acetone-d6):
d
¼0.85 (d, 3H, J¼6.3 Hz), 0.86 (d, 3H, J¼6.4 Hz), 0.96
127.7, 127.1, 126.7, 125.3, 120.0, 114.3, 77.1, 67.2, 66.4, 66.3, 53.3, 52.7 (t,
JCeN¼4.0 Hz), 48.2, 47.2, 41.5, 28.4, 24.5, 22.7, 22.4, 21.0, 20.2, 16.8.
HRMS (ESI): [Cþ] (C46H58N3O6) calcd 748.4325, found 748.4321.
(d, 3H, J¼6.6 Hz), 0.99 (d, 3H, J¼5.5 Hz), 1.37 (dd, 3H, J1¼7.1 Hz,
J2¼2.9 Hz), 1.52e1.67 (m, 6H), 1.70 (m, 1H), 1.86 (m, 2H), 2.30 (d, 3H,
J¼2.9 Hz), 3.34 (s, 9H), 3.57 (m, 2H), 4.00 (m, 2H), 4.09e4.44 (m,
5H), 4.50e4.61 (m, 2H), 6.77 (s, 1H), 6.72 (m, 1H), 6.88 (dd, 2H,
J1¼8.8 Hz, J2¼2.8 Hz), 7.11e7.49 (m, 10H), 7.57 (m, 1H), 7.66e7.78
5.3.31. [Fmoc-Val-Ile-O-MPPTMA][PF6] Fmoc-Ile-Val-O-9. Following
general procedure G using [H-Ile-O-MPPTMA][PF6] and Fmoc-Val-
OH, [Fmoc-Val-Ile-O-MPPTMA][PF6] is obtained in 94% yield as
(m, 3H), 7.87 (d, J¼7.5, 2H). 13C (75 MHz, acetone-d6):
¼171.8,
d
171.4, 171.4, 158.7, 156.6, 144.2, 141.2, 137.9, 137.2, 132.8, 129.0, 128.3,
128.3, 126.7, 126.7, 126.3, 119.9, 114.3, 77.0, 67.2, 66.5, 66.5, 60.6,
52.7 (t, JCeN¼3.7 Hz), 51.2, 48.2, 47.1, 41.1, 30.9, 28.5, 24.4, 22.6, 22.4,
a yellow oil. 1H NMR (300 MHz, acetone-d6):
1.19 (m, 1H), 1.37 (m, 1H), 1.58 (m, 2H), 1.86 (m, 2H), 1.90e2.09 (m,
d
¼0.77e0.97 (m, 12H),