Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis
Abstract
:1. Introduction
2. Isolation, Structural Features, and Biological Properties
2.1. Biphenyl Diarylheptanoids
2.1.1. Asadanin and Related Derivatives
2.1.2. Myricanone, Myricanol and Related Derivatives
2.1.3. Garuganins
2.1.4. Miscellaneous
2.2. Diphenyl Ether Diarylheptanoids
2.2.1. Acerogenins and Acerosides
2.2.2. Garuganins and Garugamblins
2.2.3. Miscellaneous
3. Total Synthesis of Biphenyl Diarylheptanoids
3.1. Biosynthetic Pathway
3.2. Total Synthesis of Biphenyl Heptanoids
3.2.1. Aryl–Aryl Bond Formation via Metal Catalyzed Coupling
3.2.2. Aryl–Aryl Bond Formation via Photochemical Cyclization
3.3. Total Synthesis of Cyclic Diphenyl Ether Heptanoids
3.3.1. Formation of Macrocycles via Oxidative Coupling
3.3.2. Formation of Macrocycles via SNAr Reaction
3.3.3. Formation of Macrocycles via Intramolecular Ullmann Ether Synthesis
3.3.4. Formation of Macrocycle via Formation of Heptane Skeleton
Via Wurtz and/or Wittig Reactions
Via Ring-Closing Metathesis
3.3.5. Enantioselective Synthesis of Diaryl Ether Heptanoids
4. Conclusion
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References and Note
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Sample Availability: Samples of the compounds 25b, 26a, 90, 96, 97, 98, and 99 are available from the authors. |
Family | Genus | Diarylheptanoids | Reference(s) | ||
---|---|---|---|---|---|
Linear (Type I) | Biphenyl (Type II) | Diphenyl Ether (Type III) | |||
Aceraceae | Acer | + | + | + | [7] |
Actinidiaceae | Clematoclethra | − | − | + | [8] |
Betulaceae | Alnus | + | + | + | [9] |
Betula | + | + | + | [10] | |
Corylus | − | + | − | [11,12] | |
Carpinus | − | + | − | [13] | |
Ostrya | − | + | − | [14] | |
Ostryopsis | + | + | + | [15,16] | |
Burseraceae | Garuga | − | + | + | [17,18] |
Boswellia | − | − | + | [19] | |
Casuarinaceae | Casuarina | − | + | − | [20] |
Juglandaceae | Engelhardia | + | − | + | [21] |
Juglans | + | + | + | [22,23] | |
Platycarya | − | + | + | [24] | |
Pterocarya | − | − | + | [25] | |
Rhoiptelea | + | + | + | [26] | |
Myricaceae | Myrica | − | + | + | [27,28] |
Morella | + | + | + | [29] | |
Rubiaceae | Scyphiphora | − | + | − | [30] |
Zingiberaceae | Alpinia | + | − | − | [31] |
Curcuma | + | − | − | [4] |
R1 | R2 | R3 | X1 | X2 | X3 | X4 | X5 | Chiral Axis | Reference and Biological Activity | |
---|---|---|---|---|---|---|---|---|---|---|
alnusonol (5a) | H | H | H | H,H | - | H,H | H,OH (S) | H | α-glucosidase inhibitor [65] | |
alnusdiol (7a) | H | H | H | H,H | OH (S) | H,H | H,OH (S) | H | aS | [51] |
5c | H | H | H | H,H | - | H,H | H,OH | OH | [53] | |
5d | H | H | H | H,H | - | H,OH | O | H | anti-adipogenic activity [55] | |
giffonin L a (7d) | H | H | H | H,OH (S) | OH (S) | H,OH (R) | H,H | OH (S) | [12] | |
giffonin M (5e) | H | H | H | H,H | - | H,OH (S) | H,H | OH (S) | [12] | |
giffonin N (5f) | H | H | H | H,H | - | H,OH (S) | H,H | O-β-d-Glc (S) | [12] | |
giffonin O (7e) | H | H | H | H,OH (R) | H | O | H,OH (R) | OH (S) | [12] | |
giffonin P a (7f) | H | H | H | H,OH (R) | OH (S) | H,OH | H,OH (S) | OH (S) | [12] | |
giffonin T (5g) | H | R′ b | H | H,H | - | H,OH (R) | H,OH (S) | OH (R) | aS | [64] |
giffonin U (7g) | H | H | H | O | OH (R) | H,OH (R) | H,OH (R) | OH (R) | aS | [64] |
carpinontriol A (5h) | H | H | H | H,OH (R) | - | H,H | H,OH (S) | OH (R) | [13] | |
carpinontriol B (5i) | H | H | H | H,H | - | H,OH (R) | H,OH (S) | OH (R) | aS | [13], inhibit lipid peroxidation [64] |
5j | OH | CH3 | H | H,H | - | H,H | H,H | H | [56], leishmanicidal (IC50 = 17 mg/mL) [63] | |
aceroside XI c (5k) | H | H | R′ b | H,H | - | H,H | H,H | H | [66] | |
acerogenin E d (5l) | H | H | H | H,H | - | H,H | H,H | H | NO production inhibitor (IC50 = 24 μM) [67] | |
acerogenin K (7h) | H | H | H | H,H | OH | H,H | H,H | H | NO production inhibitor (IC50 = 24 μM) [67] | |
ostryopsitriol (7i) | H | H | H | H,OH | OH | H,H | H,OH | H | [16] | |
betulatetraol (7j) | H | H | H | H,OH | OH | H,H | H,OH | OH | [43] |
Compound | R1 | R2 | R3 | R4 | X1 | X2 | X3 | Reference(s) and Biological Properties |
---|---|---|---|---|---|---|---|---|
11a (myricanone) | OH | CH3 | H | H | H | H | H | cytotoxicity [76,77], cell apoptosis [78], anti-inflammatory in iNOS assay (IC50 =1.0 μM) [79], radical scavenging (IC50 = 19.6 μM) [79], lowering protein tau level [71], chemo-preventive a (IC50 = 320) [80] |
11b | O-β-Glc | CH3 | H | H | H | H | H | DPPH radical scavenging activity (49.09%) [81] |
11c (alnuheptanoid B) | O-β-Glc | CH3 | COCH3 | H | H | H | H | DPPH radical scavenging activity (41.16%) [81] |
11d (saliciclaireone A) | | CH3 | H | H | H | H | H | [29] |
11e (saliciclaireone C) | OCH3 | H | | H | H | H | H | [29] |
11f | | CH3 | H | H | H | H | H | [29] |
myricananin C (11g) | H | H | H | H | H | H | H | NO release inhibition (IC50 = 64.51 μM) [82] |
myricananin E (11h) | OH | CH3 | H | OH | H | H | OCH3 | [82] |
myricananone (11i) | OH | CH3 | H | H | OH | H | H | [83] |
11j | H | CH3 | H | H | H | H | H | [84], anti-tubercular activity (IC50 = 25.8 μg/mL) [79] |
11k | OH | CH3 | H | H | H | H | OH | anti-tubercular activity (IC50 = 35.8 μg/mL) [79] |
Compound | R1 | R2 | R3 | R4 | X1 | X2 | X3 | X4 | Reference(s) and Biological Properties |
---|---|---|---|---|---|---|---|---|---|
myricanol (12a) | OH | CH3 | H | H | H | H | OH (S) | H | [68], radical scavenging (IC50 = 22.3 μM) [79], anti-Alzheimer’s disease by lowering tau level [71] |
juglanin B (12ba) | H | H | H | H | H | H | OH (S) | H | cytotoxic (HT-29) [40] |
salicireneol A (12c) | H | β-Glc | H | H | H | H | OH (S) | H | [29] |
salicireneol B (12d) | H | H | β-Glc | OH | H | H | OH (S) | H | [29] |
myricananin A (12e) | H | H | H | H | H | H | OH (S) | OH (S) | NO release inhibitor (IC50 = 45.32 μM) [82] |
myricananin B (12f) | OH | CH3 | H | H | H | H | OH (S) | OH (S) | [82] |
myricananin F (12g) | H | H | H | H | H | OH | H | H | [85] |
myricananin G (12h) | OH | CH3 | CH3 | H | H | H | OH (S) | OH (R) | [85] |
myricananin H (12i) | OCH3 | CH3 | CH3 | H | H | H | OH (S) | OH (S) | [85] |
salicimeckol (12j) | O-β-Glc | CH3 | H | H | OH | H | OH (S) | H | [29] |
12k | O-β-Glc | CH3 | H | H | H | H | OH (S) | H | anti-allergic activity [86] |
12l | | CH3 | H | H | H | H | OH (S) | H | [87], DPPH radical scavenging (IC50 = 6.8 μM) [88], SOD-like activity (IC50 = 90.5 μg/mL) [89] |
12m | | CH3 | H | H | H | H | OH (S) | [90] | |
12n | | CH3 | H | H | H | H | OH (S) | [87] |
Compound | R1 | R2 | R3 | X1 | X2 | X3 | X4 | Reference and Biological Properties |
---|---|---|---|---|---|---|---|---|
acerogenin A (23b) | H | H | H | H,H | H,H | H,OH (R) | H,H | anti-inflammatory (IC50 = 0.32 mg/ear) [107], osteogenic activity [108] |
acerogenin B (24a) | H | H | H | H,H | H,OH | H,H | H,H | cytotoxicity (IC50 = 25.1 μM) of (R)-isomer against HL60 [109], Na+-glucose cotransporter inhibitor [105] |
acerogenin C (25b) | H | H | H | H,H | H,H | O | H,H | antibacterial and neuroprotective [110], NO production inhibitor (IC50 = 61.4 μM) [111] |
acerogenin D (25c) | H | H | H | H,H | H,OH | O | H,H | radical scavenging activity (IC50 = 40 μM) [62] |
acerogenin F (23e) a | H | H | H | H,H | H,H | H,OH (R) | H,OH (R) | [60] |
acerogenin H (23f) | H | H | H | O | H,H | H,OH | H,H | [64] |
acerogenin I (24b) | H | H | H | H,H | H,OH | H,H | H,OH | [64] |
acerogenin J (23g) | H | H | H | H,H | H,H | H,OH (R) | H,OH (S) | [64] |
acerogenin L (26a) | H | H | H | H,H | O | H,H | H,H | [64] |
acerogenin M (24c) | H | H | H | O | H,OH | H,H | H,H | antitumor promoting activity [107] |
pterocarine (26b) | H | OH | H | H,H | O | H,H | H,H | cytotoxic against K562 (51% @100 μg/mL) [25] |
galeon (26c) | H | OCH3 | H | H,H | O | H,H | H,H | [104] |
10-hydroxygaleon (26d) | H | OCH3 | H | H,OH | O | H,H | H,H | [104] |
24d | H | OCH3 | H | H,H | H,OH (R) | H,H | H,H | [23] |
myricatomentogenin (26e) | H | OCH3 | OH | H,H | O | H,H | H,H | [112] |
jugcathanin (juglanin A, 26f) | CH3 | OCH3 | OH | H,H | O | H,H | H,H | cytotoxicity [40,91] |
platycarynol (24e) | CH3 | OCH3 | H | H,H | H,OH (R) | H,H | H,H | [24], cytotoxic against A549 (IC50 = 11.5 μg/mL) [22], NF-kB inhibitor [113] |
aceroside B1 (24fa) | β-d-Glc | H | H | H,H | H,OH (R) | H,H | H,H | [61], osteogenic activity [108] |
aceroside B2 (24fb) | β-d-Glc | H | H | H,H | H,OH (S) | H,H | H,H | [61] |
aceroside I (23h) | β-d-Glc | H | H | H,H | H,H | H,OH (R) | H,H | [114], osteogenic activity [108] |
aceroside II (24g) | H | H | H | H,H | H, O-β-d-Glc | H,H | H,H | [60] |
aceroside III (23i) | H | H | H | H,H | H,H | H,Y c | H,H | radical scavenging activity (IC50 = 40 μM), osteogenic activity [108] |
aceroside IV (25a) | β-d-Glc | H | H | H,H | H,H | O | H,H | [106] |
aceroside V (25d) | β-d-Glc | H | H | H,H | H,OH | O | H,H | [62] |
aceroside VI b (23j) | H | H | H | H,H | H,H | H,O-β-d-Glc | H,H | [115] |
9-oxoacerogenin A (23k) | H | H | H | H,H | O | H,OH | H,H | anti-melanogenesis (17.6% @100 μM) [109] |
maximowicziol A (24h) | H | H | H | H,H | H,OH (S) | H,H | H,OH (S) | [52] |
24i | CH3 | OCH3 | OH | H,H | H,OH | H,H | H,H | cytotoxic against A549 (IC50 = 11.5 μg/mL) [22] |
jugsigin A (24j) | H | H | OH | H,H | H,OH (S) | H,H | H,H | cytotoxic against HT-29 [116] |
2-methylacerogenin A (23l) | CH3 | H | H | H,H | H,H | H,OH (S) | H,H | [100] |
R1 | R2 | R3 | X1 | X2 | X3 | Reference | |
---|---|---|---|---|---|---|---|
giffonin A (36a) | OCH3 | OH | OCH3 | - | - | H | [11] |
giffonin B (36b) | OCH3 | OH | OCH3 | - | - | OH (S) | [11] |
giffonin C (37a) | OCH3 | OH | OCH3 | H | H,OH (R) | H | [11] |
giffonin D (37b) | OCH3 | OH | OCH3 | H | O | H | [11] |
giffonin E (37c) | OCH3 | OH | OCH3 | OH (R) | H,H | H | [11] |
giffonin F (37d) | OCH3 | OH | OCH3 | OH (R) | O | H | [11] |
giffonin G (38a) | OCH3 | OH | OCH3 | - | H,OH (S) | H | [11] |
giffonin H (38b) | H | OH | OCH3 | - | H,OH (S) | H | [11] |
giffonin J a (37e) | OCH3 | OH | OCH3 | H | H,OH (R) | OH (S) | [12] |
giffonin K (38c) | OCH3 | OH | OCH3 | - | H,OH (S) | OH (S) | [12] |
giffonin Q (39) | H | H | H | - | O | H | [132] |
giffonin R (38d) | H | H | OH | - | O | H | [132] |
giffonin S (38e) | H | OCH3 | OH | - | O | H | [132] |
Ligand | Base | Yield (%) a | Ratio (pR : pS) b |
---|---|---|---|
| Cs2CO3 | 18 | 38: 62 |
| Cs2CO3 | 22 | 44: 56 |
| Cs2CO3 | 41 | 68: 32 |
| Cs2CO3 | 34 | 57: 43 |
| K3PO4 | 39 | 72: 28 |
Solvent | Base (aq. Solution) | Yield (%) b) | Er c) |
---|---|---|---|
toluene (5 mL) | 20% CsOH | 47 | 87: 13 |
DMF (5 mL) | 20% CsOH | 90 | 50: 50 |
xylene (5 mL) | 20% CsOH | 47 | 82: 18 |
toluene (5 mL) | 20% CsF | <10 | 69: 31 |
toluene (5 mL) | 20% KOH | 17 | 64: 36 |
toluene (5 mL) | 20% CsOH | 46 | 89: 11 |
toluene (5 mL) d) | 20% CsOH | 80 | 91: 9 |
toluene (5 mL) d) | 20% CsOH | 47 | 91.5: 8.5 |
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Jahng, Y.; Park, J.G. Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis. Molecules 2018, 23, 3107. https://doi.org/10.3390/molecules23123107
Jahng Y, Park JG. Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis. Molecules. 2018; 23(12):3107. https://doi.org/10.3390/molecules23123107
Chicago/Turabian StyleJahng, Yurngdong, and Jae Gyu Park. 2018. "Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis" Molecules 23, no. 12: 3107. https://doi.org/10.3390/molecules23123107