Pennelliiside D, a New Acyl Glucose from Solanum pennellii and Chemical Synthesis of Pennelliisides
Abstract
:1. Introduction
2. Results and Discussion
2.1. Isolation and Identification of Pennelliiside D (1)
2.2. Synthesis of Pennelliiside D (1)
2.3. Root Growth-Inhibitory Activity of Pennelliiside D (1)
2.4. Synthesis of Dibenzyl Pennelliisides A and B
3. Materials and Methods
3.1. General Experimental Procedures
3.2. Plant Material
3.3. Extraction and Isolation
3.4. Synthesis of Pennelliiside D (1)
3.4.1. Synthesis of 1-O-Benzyl-2,3,4,6-O-tetraacetyl-β-D-glucose (4)
3.4.2. Synthesis of 1-O-Benzyl-β-D-glucose (5)
3.4.3. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-β-D-glucose (6)
3.4.4. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-3-O-isobutyryl-β-D-glucose (7)
3.4.5. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-3-O-isobutyryl-2-O-((S)-2-methylbutyryl)-β-D-glucose (8)
3.4.6. Synthesis of 1,6-O-Dibenzyl-3-O-isobutyryl-2-O-((S)-2-methylbutyryl)-β-D-glucose (9)
3.4.7. Synthesis of 1,6-O-Dibenzyl-3,4-O-diisobutyryl-2-O-((S)-2-methylbutyryl)-β-D-glucose (2)
3.4.8. Removal of Benzyl Ether
3.5. Synthesis of Pennelliisides A and B
3.5.1. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-2,3-O-diisobutyryl-β-D-glucose (13)
3.5.2. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-3-O-(8-methylnonanoyl)-β-D-glucose (14)
3.5.3. Synthesis of 1-O-Benzyl-4,6-O-benzylidine-2-O-isobutyryl-3-O-(8-methylnonanoyl)-β-D-glucose (15)
3.5.4. Synthesis of 16a, b and 17a, b
3.6. Root Growth-Inhibitory Activity
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Position | Type | Natural Dibenzyl Pennelliiside D (2) | |
---|---|---|---|
δC | δH (J in Hz) | ||
1 | CH | 100.3 | 4.38, d (7.6) |
2 | CH | 71.9 | 5.46, m |
3 | CH | 73.5 | 5.48, m |
4 | CH | 70.1 | 5.30, dd (10.7, 9.5) |
5 | CH | 74.3 | 3.42, m |
6 | CH2 | 69.9 | 3.47, m |
1a′ | CH2 | 70.7 | 4.75, d (12.2) |
1b′ | 4.45, d (12.2) | ||
2′ | C | 138.0 | |
3′ | CH | 128.1–128.6 | 7.26, t (7.4) |
4′ | CH | 128.1–128.6 | 7.12–7.19, m |
5′ | CH | 128.1–128.6 | 7.08, t (7.3) |
6′ | CH | 128.1–128.6 | 7.12–7.19, m |
7′ | CH | 128.1–128.6 | 7.26, t (7.4) |
1 | C | 174.7 | |
A2 | CH | 41.86 | 2.28, m |
A3 | CH3 | 17.2 | 1.08, d (7.0) |
A4 | CH2 | 27.2 | 1.32, 1.69, m, m |
A5 | CH3 | 12.2 | 0.81, t (7.4) |
B1 | C | 176.2 | |
B2 | CH | 34.6 | 2.41, m |
B3 | CH3 | 19.2–19.5 | 1.08, d (7.0) |
B4 | CH3 | 19.2–19.5 | 1.08, d (7.0) |
C1 | C | 175.3 | |
C2 | CH | 34.5 | 2.31, m |
C3 | CH3 | 19.2–19.5 | 1.02, d (7.0) |
C4 | CH3 | 19.2–19.5 | 0.98, d (7.0) |
1a″ | CH2 | 73.9 | 4.33, d (5.5) |
1b″ | 4.33, d (5.5) | ||
2″ | C | 139.0 | |
3″ | CH | 128.1–128.7 | 7.26, t (7.4) |
4″ | CH | 128.1–128.7 | 7.12–7.19, m |
5″ | CH | 128.1–128.7 | 7.08, t (7.3) |
6″ | CH | 128.1–128.7 | 7.12–7.19, m |
7″ | CH | 128.1–128.7 | 7.26, t (7.4) |
Position | α Anomer | β Anomer | |||
---|---|---|---|---|---|
Type | δC | δH (J in Hz) | δC | δH (J in Hz) | |
1 | CH | 90.4 | 5.48, d (3.6) | 96.1 | 4.76, d (6.9) |
2 | CH | 71.4 | 4.85, dd (6.8, 3.6) | 73.5 | 4.91, dd (7.7, 6.89) |
3 | CH | 69.0 | 5.65, dd (10.9, 9.9) | 71.4 | 5.41, dd (10.4, 9.6) |
4 | CH | 68.8 | 5.01, dd (10.9, 9.7) | 68.8 | 5.09, dd (10.4, 8.1) |
5 | CH | 69.7 | 4.06, m | 74.7 | 3.59, m |
6 | CH2 | 61.3 | 3.71, 3.55, m | 61.3 | 3.75, 3.59, m |
A1 | C | 176.6 | 176.6 | ||
A2 | CH | 41.1 | 2.38, m | 41.1 | 2.42, m |
A3 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.07–1.21, m |
A4 | CH2 | 26.7 | 1.41, 1.62, m | 26.7 | 1.45, 1.66, m |
A5 | CH3 | 11.7 | 0.85, m | 11.7 | 0.90, m |
B1 | C | 176.0 | 176.0 | ||
B2 | CH | 34.2 | 2.50, m | 34.2 | 2.50, m |
B3 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.07–1.21, m |
B4 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.07–1.21, m |
C1 | C | 176.9 | 176.9 | ||
C2 | CH | 34.2 | 2.56, m | 34.2 | 2.56, m |
C3 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.07–1.21, m |
C4 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.07–1.21, m |
Position. | Type | α Anomer | β Anomer | ||
---|---|---|---|---|---|
δC | δH (J in Hz) | δC | δH (J in Hz) | ||
1 | CH | 90.4 | 5.48, d (3.6) | 96.1 | 4.72, d (6.9) |
2 | CH | 71.4 | 4.85, dd (6.8, 3.6) | 73.5 | 4.87, dd (7.7, 6.89) |
3 | CH | 69.0 | 5.65, dd (10.9, 9.9) | 71.4 | 5.37, dd (10.4, 9.6) |
4 | CH | 68.8 | 5.01, dd (10.9, 9.7) | 68.8 | 5.05, dd (10.4, 8.1) |
5 | CH | 69.7 | 4.06, m | 74.7 | 3.55, m |
6 | CH2 | 61.3 | 3.71, 3.55, m | 61.3 | 3.71, 3.55, m |
A1 | C | 176.6 | 176.6 | ||
A2 | CH | 41.1 | 2.24–2.42, m | 41.1 | 2.24–2.42, m |
A3 | CH3 | 16.4–19.4 | 1.03-1.17, m | 16.4–19.4 | 1.03-1.17, m |
A4 | CH2 | 26.7 | 1.41, 1.62, m | 26.7 | 1.41, 1.62, m |
A5 | CH3 | 11.7 | 0.85, m | 11.7 | 0.85, m |
B1 | C | 176.0 | 176.0 | ||
B2 | CH | 34.2 | 2.50, m | 34.2 | 2.50, m |
B3 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.03–1.17, m |
B4 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.03–1.17, m |
C1 | C | 176.9 | 176.9 | ||
C2 | CH | 34.2 | 2.56, m | 34.2 | 2.52, m |
C3 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.03–1.17, m |
C4 | CH3 | 16.4–19.4 | 1.03–1.17, m | 16.4–19.4 | 1.03–1.17, m |
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Masimbula, R.; Kobayashi, H.; Nakashima, T.; Nambu, Y.; Kitaoka, N.; Matsuura, H. Pennelliiside D, a New Acyl Glucose from Solanum pennellii and Chemical Synthesis of Pennelliisides. Molecules 2022, 27, 3728. https://doi.org/10.3390/molecules27123728
Masimbula R, Kobayashi H, Nakashima T, Nambu Y, Kitaoka N, Matsuura H. Pennelliiside D, a New Acyl Glucose from Solanum pennellii and Chemical Synthesis of Pennelliisides. Molecules. 2022; 27(12):3728. https://doi.org/10.3390/molecules27123728
Chicago/Turabian StyleMasimbula, Rishni, Hiroto Kobayashi, Tenki Nakashima, Yurika Nambu, Naoki Kitaoka, and Hideyuki Matsuura. 2022. "Pennelliiside D, a New Acyl Glucose from Solanum pennellii and Chemical Synthesis of Pennelliisides" Molecules 27, no. 12: 3728. https://doi.org/10.3390/molecules27123728