Divergent Synthesis of Four Monomeric Ellagitannins toward the Total Synthesis of an Oligomeric Ellagitannin, Nobotanin K
Abstract
:1. Introduction
2. Results and Discussion
3. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Appendix A
1H NMR Data for Nobotanin D (5) in Acetone-d6 + D2O | |||
---|---|---|---|
Assignment | Natural Product | Synthetic Product | Δ(Natural–Syn.) |
δ | δ | δ | |
galloyl | 7.13 | 7.13 | 0.00 |
galloyl | 7.12 | 7.12 | 0.00 |
HHDP | 6.70 | 6.71 | −0.01 |
HHDP | 6.42 | 6.42 | 0.00 |
H-1 | 6.17 | 6.16 | 0.00 |
H-3 | 5.24 | 5.24 | 0.00 |
H-2 | 5.06 | 5.06 | 0.00 |
H-6 | 4.61 | 4.61 | −0.01 |
H-6 | 4.46 | 4.46 | 0.00 |
H-5 | 4.08 | 4.08 | 0.00 |
H-4 | 4.00 | 4.00 | −0.01 |
Specific optical rotation for nobotanin D (5) in MeOH (unit of c: mg/mL) | |||
natural product (c = 0.08, 25 °C) | synthetic product (c = 0.09, 25 °C) | ||
18 | 20 |
1H NMR Data for Pterocarinin C (3) in Acetone-d6 | |||||
---|---|---|---|---|---|
Natural Product | Our Synthetic Product | Kawabata Group’s Synthetic Product [38] | Δ(Natural–Ours) | Δ(Kawa.–Ours) | |
Assignment | δ | δ | δ | δ | δ |
galloyl | 7.18 | 7.18 | 7.17 | 0.00 | −0.01 |
galloyl | 7.17 | 7.17 | 7.17 | 0.00 | 0 |
galloyl | 7.14 | 7.14 | 7.15 | 0.00 | 0.01 |
HHDP | 6.47 | 6.46 | 6.46 | 0.01 | 0 |
HHDP | 6.44 | 6.43 | 6.44 | 0.01 | 0.01 |
H-1 | 6.36 | 6.36 | 6.35 | 0.00 | −0.01 |
H-4 | 5.65–5.58 | 5.65–5.59 | 5.64–5.58 | 0–(−0.01) | (−0.01)–(−0.01) |
H-3 | |||||
H-2 | 5.21 | 5.22 | 5.21 | −0.01 | −0.01 |
H-6 | 4.56 | 4.56 | 4.56 | 0.00 | 0 |
H-5 | 4.52 | 4.52 | 4.53–4.51 | 0.00 | 0 |
H-6 | 4.39 | 4.39 | 4.40 | 0.00 | 0.01 |
Specific optical rotation for pterocarinin C (3) in acetone (unit of c: mg/mL) | |||||
natural product (c = 0.07, 25 °C) | Kawabata group [39] (c = 0.8, 20 °C) | ours (c = 1.0, 25 °C) | |||
18 | 59 | 56 |
1H NMR Data for Casuarictin (3) in Acetone-d6 | |||
---|---|---|---|
Assignment | Literature Data [25] | Synthetic Product | Δ(Lit.–Syn.) |
δ | δ | δ | |
galloyl | 7.18 | 7.18 | 0.00 |
HHDP | 6.68 | 6.67 | 0.01 |
HHDP | 6.55 | 6.54 | 0.01 |
HHDP | 6.47 | 6.46 | 0.01 |
HHDP | 6.38 | 6.37 | 0.01 |
H-1 | 6.22 | 6.22 | 0.00 |
H-3 | 5.45 | 5.45 | 0.00 |
H-6 | 5.37 | 5.37 | 0.00 |
H-4 | 5.18 | 5.19 | −0.01 |
H-2 | 5.17 | 5.18 | −0.01 |
H-5 | 4.50 | 4.51 | −0.01 |
H-6 | 3.88 | 3.88 | 0.00 |
Specific optical rotation for casuarictin (3) in MeOH (unit of c: mg/mL) | |||
literature data [23] a (c = 0.2) | synthetic product (c = 0.12, 23 °C) | ||
35 | 26 |
1H NMR Data for Rugosin C (3) in Acetone-d6 | |||
---|---|---|---|
Assignment | Literature Data [23] | Synthetic Product | Δ(Lit.–Syn.) |
δ | δ | δ | |
galloyl | 7.15 | 7.15 | 0.00 |
HHDP or valoneoyl | 7.14 | 7.14 | 0.00 |
HHDP or valoneoyl | 6.54 | 6.54 | 0.00 |
HHDP or valoneoyl | 6.46 | 6.45 | 0.01 |
HHDP or valoneoyl | 6.40 | 6.40 | 0.00 |
HHDP or valoneoyl | 6.34 | 6.38 | −0.04 |
H-1 | 6.18 | 6.19 | −0.01 |
H-3 | 5.44 | 5.44 | 0.00 |
H-6 | 5.28 | 5.28 | 0.00 |
H-4 | 5.14 | 5.14 | 0.00 |
H-2 | 5.07 | 5.07 | 0.00 |
H-5 | 4.46 | 4.46 | 0.00 |
H-6 | 3.79 | 3.79 | 0.00 |
1H NMR Data for Permethylated Rugosin C (32) in Acetone-d6 | ||||
---|---|---|---|---|
Assignment | Number of Protons | Literature Data [3] | Synthetic Product | Δ(Lit.–Syn.) |
δ | δ | δ | ||
galloyl | 2 | 7.31 | 7.32 | −0.01 |
valoneoyl | 1 | 7.25 | 7.25 | 0.00 |
HHDP and valoneoyl | 1 | 6.85 | 6.83 | 0.02 |
1 | 6.83 | 6.83 | 0.00 | |
HHDP | 1 | 6.69 | 6.69 | 0.00 |
valoneoyl | 1 | 6.50 | 6.50 | 0.00 |
H-1 | 1 | 6.26 | 6.26 | 0.00 |
H-3 | 1 | 5.55 | 5.54 | 0.01 |
H-2 | 1 | 5.23 | 5.22 | 0.01 |
H-6 | 1 | 5.15 | 5.16 | −0.01 |
H-4 | 1 | 5.06 | 5.07 | −0.01 |
H-5 | 1 | 4.39 | 4.42 | −0.03 |
O-Me | 3 | 4.06 | 4.06 | 0.00 |
O-Me | 3 | 3.90 | 3.90 | 0.00 |
O-Me | 3 | 3.89 | 3.89 | 0.00 |
O-Me | 3 | 3.89 | 0.00 | |
O-Me | 6 | 3.87 | 3.87 | 0.00 |
O-Me | 3 | 3.86 | 3.86 | 0.00 |
O-Me | 3 | 3.85 | 3.86 | −0.01 |
O-Me | 3 | 3.83 | 3.83 | 0.00 |
O-Me | 3 | 3.80 | 3.82 | −0.02 |
O-Me | 3 | 3.80 | 0.00 | |
O-Me | 3 | 3.76 | 3.77 | −0.01 |
O-Me | 3 | 3.76 | 0.00 | |
O-Me | 3 | 3.76 | 0.00 | |
O-Me | 3 | 3.74 | 3.74 | 0.00 |
O-Me | 3 | 3.70 | 3.70 | 0.00 |
O-Me | 3 | 3.66 | 3.65 | 0.01 |
O-Me | 3 | 3.58 | 3.60 | −0.02 |
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Hashimoto, H.; Wakamori, S.; Ikeuchi, K.; Yamada, H. Divergent Synthesis of Four Monomeric Ellagitannins toward the Total Synthesis of an Oligomeric Ellagitannin, Nobotanin K. Organics 2022, 3, 293-303. https://0-doi-org.brum.beds.ac.uk/10.3390/org3030022
Hashimoto H, Wakamori S, Ikeuchi K, Yamada H. Divergent Synthesis of Four Monomeric Ellagitannins toward the Total Synthesis of an Oligomeric Ellagitannin, Nobotanin K. Organics. 2022; 3(3):293-303. https://0-doi-org.brum.beds.ac.uk/10.3390/org3030022
Chicago/Turabian StyleHashimoto, Hajime, Shinnosuke Wakamori, Kazutada Ikeuchi, and Hidetoshi Yamada. 2022. "Divergent Synthesis of Four Monomeric Ellagitannins toward the Total Synthesis of an Oligomeric Ellagitannin, Nobotanin K" Organics 3, no. 3: 293-303. https://0-doi-org.brum.beds.ac.uk/10.3390/org3030022