Procyanidin C2

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Procyanidin C2
Procyanidin C2.svg
Names
IUPAC name
[(2R,3S,4S)-Flavan-3,3′,4′,5,7-pentol]-(4→8)-[(2R,3S,4R)-flavan-3,3′,4′,5,7-pentol]-(4→8)-[(2R,3S)-flavan-3,3′,4′,5,7-pentol]
Preferred IUPAC name
(12R,13S,14S,22R,23S,24R,32R,33S)-12,22,32-Tris(3,4-dihydroxyphenyl)-13,14,23,24,33,34-hexahydro-12H,22H,32H-[14,28:24,38-ter-1-benzopyran]-13,15,17,23,25,27,33,35,37-nonol
Other names
C-(4,8)-C-(4,8)-C
Procyanidin trimer C2
Catechin-(4alpha→8)-Catechin-(4alpha→8)-Catechin
Catechin-(4α→8)-catechin-(4α→8)-catechin
Trimer C2
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/C45H38O18/c46-18-10-27(54)33-32(11-18)61-42(16-2-5-21(48)25(52)8-16)39(59)37(33)35-29(56)14-30(57)36-38(40(60)43(63-45(35)36)17-3-6-22(49)26(53)9-17)34-28(55)13-23(50)19-12-31(58)41(62-44(19)34)15-1-4-20(47)24(51)7-15/h1-11,13-14,31,37-43,46-60H,12H2/t31-,37-,38+,39-,40-,41+,42+,43+/m0/s1
    Key: MOJZMWJRUKIQGL-WNCKYJNFSA-N
  • Oc8ccc(cc8O)C(C1O)Oc7cc(O)cc(O)c7C1c3c(O)cc(O)c(c3OC(C5O)c(cc2O)ccc2O)C5c4c6OC(c(cc9O)ccc9O)C(O)Cc6c(O)cc4O
Properties
C45H38O18
Molar mass 866.74 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Procyanidin C2 is a B type proanthocyanidin trimer, a type of condensed tannin.

Contents

Natural occurrences

Procyanidin C2 is found in grape seeds (Vitis vinifera) [1] [2] and wine, [3] in barley (Hordeum vulgare), [4] malt [5] and beer, [6] in Betula spp., in Pinus radiata , in Potentilla viscosa , in Salix caprea or in Cryptomeria japonica . [7] [8] [9]

The contents in barley grain of trimeric proanthocyanidins, including procyanidin C2, range from 53 to 151 μg catechin equivalents/g. [10]

Possible health uses

Proanthocyanidin oligomers, extracted from grape seeds, have been used for the experimental treatment of androgenic alopecia. When applied topically, they promote hair growth in vitro, and induce anagen in vivo. Procyanidin C2 is the subtype of extract most effective. [11]

Experiments showed that both procyanidin C2 and Pycnogenol (French maritime pine bark extract) increase TNF-α secretion in a concentration- and time-dependent manner. These results demonstrate that procyanidins act as modulators of the immune response in macrophages. [12]

Chemistry

In the presence of procyanidin C2, the red color of the anthocyanin oenin appears more stable. However, the HPLC chromatogram shows a decrease in the amplitude of the peaks of oenin and procyanidin C2. Concomitantly, a new peak appears with a maximal absorption in the red region. This newly formed pigment probably comes from the condensation of oenin and procyanidin C2. [13]

Chemical synthesis

A stereoselective synthesis of benzylated catechin trimer under intermolecular condensation is achieved using equimolar amount of dimeric catechin nucleophile and monomeric catechin electrophile catalyzed by AgOTf or AgBF4. The coupled product can be transformed into procyanidin C2 by a known procedure. [14]

The stereoselective synthesis of seven benzylated proanthocyanidin trimers (epicatechin-(4β-8)-epicatechin-(4β-8)-epicatechin trimer (procyanidin C1), catechin-(4α-8)-catechin-(4α-8)-catechin trimer (procyanidin C2), epicatechin-(4β-8)-epicatechin-(4β-8)-catechin trimer and epicatechin-(4β-8)-catechin-(4α-8)-epicatechin trimer derivatives) can be achieved with TMSOTf-catalyzed condensation reaction, in excellent yields. The structure of benzylated procyanidin C2 was confirmed by comparing the 1H NMR spectra of protected procyanidin C2 that was synthesized by two different condensation approaches. Finally, deprotection of (+)-catechin and (−)-epicatechin trimers derivatives gives four natural procyanidin trimers in good yields. [15]

Molar equivalents of synthetic (2R,3S,4R or S)-leucocyanidin and (+)-catechin condense with exceptional rapidity at pH 5 under ambient conditions to give the all-trans-[4,8]- and [4,6]-bi-[(+)-catechins] (procyanidins B3, B6) the all-trans-[4,8:4,8]- and [4,8:4,6]-tri-[(+)-catechins] (procyanidin C2 and isomer). [16]

Iterative oligomer chemical synthesis

A coupling utilising a C8-boronic acid as a directing group was developed in the synthesis of natural procyanidin B3 (i.e., 3,4-trans-(+)-catechin-4α→8-(+)-catechin dimer). The key interflavan bond is forged using a Lewis acid-promoted coupling of C4-ether with C8-boronic acid to provide the α-linked dimer with high diastereoselectivity. Through the use of a boron protecting group, the coupling procedure can be extended to the synthesis of a protected procyanidin trimer analogous to natural procyanidin C2. [17]

See also

Related Research Articles

<span class="mw-page-title-main">Flavan-3-ol</span> Category of polyphenol compound

Flavan-3-ols are a subgroup of flavonoids. They are derivatives of flavans that possess a 2-phenyl-3,4-dihydro-2H-chromen-3-ol skeleton. Flavan-3-ols are structurally diverse and include a range of compounds, such as catechin, epicatechin gallate, epigallocatechin, epigallocatechin gallate, proanthocyanidins, theaflavins, thearubigins. They play a part in plant defense and are present in the majority of plants.

<span class="mw-page-title-main">Catechin</span> Type of natural phenol as a plant secondary metabolite

Catechin is a flavan-3-ol, a type of secondary metabolite providing antioxidant roles in plants. It belongs to the subgroup of polyphenols called flavonoids.

Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex polyphenols, having the same polymeric building block, form the group of tannins.

<span class="mw-page-title-main">Procyanidin</span>

Procyanidins are members of the proanthocyanidin class of flavonoids. They are oligomeric compounds, formed from catechin and epicatechin molecules. They yield cyanidin when depolymerized under oxidative conditions.

<span class="mw-page-title-main">Phenolic content in wine</span> Wine chemistry

The phenolic content in wine refers to the phenolic compounds—natural phenol and polyphenols—in wine, which include a large group of several hundred chemical compounds that affect the taste, color and mouthfeel of wine. These compounds include phenolic acids, stilbenoids, flavonols, dihydroflavonols, anthocyanins, flavanol monomers (catechins) and flavanol polymers (proanthocyanidins). This large group of natural phenols can be broadly separated into two categories, flavonoids and non-flavonoids. Flavonoids include the anthocyanins and tannins which contribute to the color and mouthfeel of the wine. The non-flavonoids include the stilbenoids such as resveratrol and phenolic acids such as benzoic, caffeic and cinnamic acids.

<span class="mw-page-title-main">Prodelphinidin</span>

Prodelphinidin is a name for the polymeric tannins composed of gallocatechin. It yields delphinidin during depolymerisation under oxidative conditions.

<span class="mw-page-title-main">Prodelphinidin B3</span> Chemical compound

Prodelphinidin B3 is a prodelphinidin dimer found in food products such as barley and beer, in fruits and pod vegetables. It can also be found in pomegranate peels.

<span class="mw-page-title-main">Leucocyanidin</span> Chemical compound

Leucocyanidin is a colorless chemical compound that is a member of the class of natural products known as leucoanthocyanidins.

<span class="mw-page-title-main">Oenin</span> Chemical compound

Oenin is an anthocyanin. It is the 3-glucoside of malvidin. It is one of the red pigments found in the skin of purple grapes and in wine.

<span class="mw-page-title-main">Procyanidin B2</span> Chemical compound

Procyanidin B2 is a B type proanthocyanidin. Its structure is (−)-Epicatechin-(4β→8)-(−)-epicatechin.

A type proanthocyanidins are a specific type of proanthocyanidins, which are a class of flavonoid. Proanthocyanidins fall under a wide range of names in the nutritional and scientific vernacular, including oligomeric proanthocyanidins, flavonoids, polyphenols, condensed tannins, and OPCs. Proanthocyanidins were first popularized by French scientist Jacques Masquelier.

<span class="mw-page-title-main">Procyanidin B1</span> Chemical compound

Procyanidin B1 is a procyanidin dimer.

<span class="mw-page-title-main">Procyanidin B3</span> Chemical compound

Procyanidin B3 is a B type proanthocyanidin. Procyanidin B3 is a catechin dimer.

<span class="mw-page-title-main">Procyanidin B4</span> Chemical compound

Procyanidin B4 is a B type proanthocyanidin.

<span class="mw-page-title-main">Procyanidin B5</span> Chemical compound

Procyanidin B5 is a B type proanthocyanidin.

<span class="mw-page-title-main">Procyanidin B6</span> Chemical compound

Procyanidin B6 is a B type proanthocyanidin.

<span class="mw-page-title-main">Procyanidin B8</span> Chemical compound

Procyanidin B8 is a B type proanthocyanidin.

<span class="mw-page-title-main">Procyanidin C1</span> Chemical compound

Procyanidin C1 (PCC1) is a B type proanthocyanidin. It is an epicatechin trimer found in grape, unripe apples, and cinnamon.

<span class="mw-page-title-main">Condensed tannin</span> Polymers formed by the condensation of flavans.

Condensed tannins are polymers formed by the condensation of flavans. They do not contain sugar residues.

B type proanthocyanidins are a specific type of proanthocyanidin, which are a class of flavanoids. They are oligomers of flavan-3-ols.

References

  1. ↑ Romeyer FM, Macheix JJ, Sapis JC (1985). "Changes and importance of oligomeric procyanidins during maturation of grape seeds". Phytochemistry. 25 (1): 219–221. Bibcode:1985PChem..25..219R. doi:10.1016/S0031-9422(00)94532-1.
  2. ↑ Tsang C, Auger C, Mullen W, Bornet A, Rouanet JM, Crozier A, Teissedre PL (August 2005). "The absorption, metabolism and excretion of flavan-3-ols and procyanidins following the ingestion of a grape seed extract by rats". The British Journal of Nutrition. 94 (2): 170–81. doi: 10.1079/BJN20051480 . PMID   16115350.
  3. ↑ Identification of the condensed tannins content in grape and Bordeaux wine by means of standards of synthesis. S. Fabre, E. Fouquet, I. Pianet and P-L. Teissedre (article Archived 2016-03-04 at the Wayback Machine )
  4. ↑ Kristiansen KN (1984). "Biosynthesis of proanthocyanidins in barley: Genetic control of the conversion of dihydroquercetin to catechin and procyanidins". Carlsberg Research Communications. 49 (5): 503–524. doi: 10.1007/BF02907552 .
  5. ↑ Goupy P, Hugues M, Boivin P, Amiot MJ (1999). "Antioxidant composition and activity of barley (Hordeum vulgare) and malt extracts and of isolated phenolic compounds". Journal of the Science of Food and Agriculture. 79 (12): 1625–1634. doi:10.1002/(SICI)1097-0010(199909)79:12<1625::AID-JSFA411>3.0.CO;2-8.
  6. ↑ McMurrough I, Madigan D, Smyth MR (1996). "Semipreparative Chromatographic Procedure for the Isolation of Dimeric and Trimeric Proanthocyanidins from Barley". Journal of Agricultural and Food Chemistry. 44 (7): 1731–1735. doi:10.1021/jf960139m.
  7. ↑ Harborne JB, Baxter H (1999). "Flavans and Proanthocyanidins". The Handbook of Natural Flavonoids. Vol. 2. Chichester: Wiley. p. 355. ISBN   978-0-471-95893-2.
  8. ↑ Thompson RS, Jacques D, Haslam E, Tanner RJ (1972). "Plant proanthocyanidins. Part I. Introduction; the isolation, structure, and distribution in nature of plant procyanidins". Journal of the Chemical Society, Perkin Transactions 1: 1387. doi:10.1039/P19720001387.
  9. ↑ Brandon MJ, Foo LY, Porter LJ, Meredith P (1980). "Proanthocyanidins of barley and sorghum; composition as a function of maturity of barley ears". Phytochemistry. 21 (12): 2953–2957. Bibcode:1980PChem..21.2953B. doi:10.1016/0031-9422(80)85076-X.
  10. ↑ Quinde-Axtell Z, Baik BK (December 2006). "Phenolic compounds of barley grain and their implication in food product discoloration". Journal of Agricultural and Food Chemistry. 54 (26): 9978–84. doi:10.1021/jf060974w. PMID   17177530.
  11. ↑ Takahashi T, Kamiya T, Hasegawa A, Yokoo Y (March 1999). "Procyanidin oligomers selectively and intensively promote proliferation of mouse hair epithelial cells in vitro and activate hair follicle growth in vivo". The Journal of Investigative Dermatology. 112 (3): 310–6. doi: 10.1046/j.1523-1747.1999.00532.x . PMID   10084307.
  12. ↑ Park YC, Rimbach G, Saliou C, Valacchi G, Packer L (January 2000). "Activity of monomeric, dimeric, and trimeric flavonoids on NO production, TNF-alpha secretion, and NF-kappaB-dependent gene expression in RAW 264.7 macrophages". FEBS Letters. 465 (2–3): 93–7. doi: 10.1016/S0014-5793(99)01735-4 . PMID   10631311.
  13. ↑ Malien-Aubert C, Dangles O, Amiot MJ (May 2002). "Influence of procyanidins on the color stability of oenin solutions". Journal of Agricultural and Food Chemistry. 50 (11): 3299–305. doi:10.1021/jf011392b. PMID   12010001.
  14. ↑ Makabe H, Oizumi Y, Mohri Y, Hattori Y (2011). "Efficient Stereoselective Synthesis of Catechin Trimer Derivative Using Silver Lewis Acid-Mediated Equimolar Condensation". Heterocycles. 83 (4): 739. doi:10.3987/COM-11-12159 (inactive 2024-02-17). hdl: 10091/16138 .{{cite journal}}: CS1 maint: DOI inactive as of February 2024 (link)
  15. ↑ Nakajima N, Saito A, Tanaka A, Ubukata M (2004). "Efficient Stereoselective Synthesis of Proanthocyanidin Trimers with TMSOTf-Catalyzed Intermolecular Condensation". Synlett (6): 1069–1073. doi:10.1055/s-2004-822905.
  16. ↑ Delcour JA, Ferreira D, Roux DG (1983). "Synthesis of condensed tannins. Part 9. The condensation sequence of leucocyanidin with (+)-catechin and with the resultant procyanidins". Journal of the Chemical Society, Perkin Transactions 1: 1711. doi:10.1039/P19830001711.
  17. ↑ Dennis EG, Jeffery DW, Johnston MR, Perkins MV, Smith PA (2012). "Procyanidin oligomers. A new method for 4→8 interflavan bond formation using C8-boronic acids and iterative oligomer synthesis through a boron-protection strategy". Tetrahedron. 68: 340–348. doi:10.1016/j.tet.2011.10.039. hdl: 2440/76362 . INIST   25254810.
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