龙脷叶中天然产物sauropunol <b>A</b>-<b>D</b>的全合成

王子豪; 王诚倩; 徐进宜; 吴晓明; 谢唯佳

doi:10.11665/j.issn.1000-5048.20170407

龙脷叶中天然产物sauropunol A-D的全合成

1.
中国药科大学药物科学研究院
2.
药物化学教研室

基金项目: 国家自然科学基金资助项目(No.81473081,No.81673312)

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- 刊出日期: 2017-08-24

Total synthesis of sauropunol A-D isolated from Sauropus rostratus genus plants

WANG Zihao¹,

WANG Chengqian²,

XU Jinyi²,

WU Xiaoming¹,

XIE Weijia²

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摘要

摘要: Sauropunol A - D 是从中药龙脷叶中分离出的具有2-脱氧-3，6脱水呋喃己糖(苷)结构的化学成分，具有潜在抗炎、抗菌等生物活性。以2-脱氧-D-阿拉伯己糖为起始原料，经多步反应获得3，5-位以对甲氧基苄基保护的伯醇中间体，对其进行三氟甲磺酰化所得的三氟甲磺酸酯中间体会自动引发分子内关环反应从而构建2-脱氧-3，6-脱水-D-葡萄糖呋喃糖苷骨架结构。经脱保护反应，最终合成了sauropunol A ， B和C/D ，总产率分别为21%，5%和17%(互变异构体sauropunol C/D )。基于前期文献报道，对这4个化合物(sauropunol A - D )的结构进行了确证。

关键词:
龙脷叶 /

sauropunol A-D /

3,6-脱水己糖结构 /

分子内环化反应 /

天然产物 /

全合成

Abstract: Sauropunol A-D potentially with anti-inflammatory, anti-bacterial activities were recently isolated from traditional Chinese medicinal plant Sauropus rostratus. Herein, we report the total synthesis of sauropunol( A - D )starting from a commercially available 2-deoxy-D-arabino-hexopyranose. The trifluoromethane sulfonation of intermediates could simultaneously trigger intramolecular cyclization to afford 3, 6-anhydro hexofuranoside scaffold. The following deprotection reaction could produce sauropunol A , B and C / D with total yields of 21%, 5%, and 17%(isomer sauropunol C / D ), respectively. Structures of the target compounds were confirmed by comparison with NMR spectroscopic properties of those previously reported.

Keywords:
Sauropus rostratus /

sauropunol A-D /

3,6-anhydrohexosides /

intramolecular cyclization /

natural products /

total synthesis

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参考文献(16)

[1] Wang PH,Lee SS.Active chemical constituents from Sauropus androgynus[J].J Chin Chem Soc,1997,44(2):145-149.

[2] Rao SN,Vasanth S,Pattabhi V.Lup-1,20(29)-dien-3-one,a triterpenoid from Agyneia bacciformis,A.Juss[J].Acta Crystallogr,2004,60(6):1092-1093.

[3] Lu C, Bai L, Shen Y. Five unusual natural carbohydrates from Actinosynnema pretiosum[J].Chem Nat Comp,2008,44(5):594-597.

[4] Bredt DS,Snyder SH.Nitric oxide,a physiological messenger molecule[J].Annu Rev Biochem,1994,63:175-195.

[5] Kojda G,Kottenberg K.Regulation of basal myocardial function by NO[J].Cardiovasc Res,1999,41(3):514-523.

[6] Nathan C,Xie Q.Nitric oxide synthases:roles,tolls,and controls[J].Cell,1994,78(6):915-918.

[7] Wang CH,Wen L,Liu HL,et al.Five natural carbohydrates from the leaves of Sauropus rostratus[J].Carbohydr Res,2013,384(1):99-101.

[8] Yang K,Wang Z,Brenner T,et al.Sucrose release from agar gels:effects of dissolution order and the network in homogeneity[J].Food Hydrocolloids,2015,43:100-106.

[9] Kikuchi H,Saito Y,Komiya J,et al.Furanodictine A and B:amino sugar analogues produced by cellular slime mold dictyostelium discoideum showing neuronal differentiation activity[J].J Org Chem,2001,66(21):6982-6987.

[10] Saulnier MG,Langley DR,Frennesson DB,et al.Novel 3′,6′-anhydro and N12,N13-bridged glycosylated fluoroindolo[2,3-a]carbazoles as topoisomerase I inhibitors.Fluorine as a leaving group from sp³ carbon[J].Org Lett,2005,7(7):1271-1274.

[11] Shiraiwa K,Yuan S,Fujiyama A,et al.Benzyl benzoate glycoside and 3-deoxy-D-manno-2-octulosonic acid derivatives from Solidago decurrens[J].J Nat Prod,2011,75(1):88-92.

[12] Fujita K,Yamamura H,Imoto T,et al.Synthesis of 6A,6X-di-O-(p-tosyl)-.gamma.-cyclodextrins and their structural determination through enzymic hydrolysis of 3A,6A;3X,6X-dianhydro-γ-cyclodextrins[J].J Org Chem,1988,53(9):1943.

[13] Fujita K,Tahara T,Yamamura H,et al.Specific preparation and structure determination of 3A,3C,3E-tri-O-sulfonyl-β-cyclodextrin[J].J Org Chem,1990,55(3):877.

[14] Jadhav V,Pedersen CM,Bols M.A study of anhydrocellulosesis a cellulose structure with residues in a ¹C₄conformation more prone to hydrolysis[J].Org Biomol Chem,2011,9(21):7525.

[15] Liu L,Wang CQ,Liu D,et al.Construction of 3,6-anhydrohexosides via intramolecular cyclization of triflates and its application to the synthesis of natural product isolated from leaves of Sauropus rostratus[J].Org Lett,2014,16(19):5004-5007.

[16] Zhang CX,Wang CQ,Wang ZH,et al.Total synthesis,structural elucidation and anti-inflammatory activity evaluation of 2-deoxy-3,6-anhydro hexofuranoside derivatives isolated from Sauropus rostratus[J].Org Biomol Chem,2016,14(46):10906-10913.

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文章访问数: 1049

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PDF下载量: 1409

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刊出日期: 2017-08-24

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参考文献(16)
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[1]	Wang PH,Lee SS.Active chemical constituents from Sauropus androgynus[J].J Chin Chem Soc,1997,44(2):145-149.
[2]	Rao SN,Vasanth S,Pattabhi V.Lup-1,20(29)-dien-3-one,a triterpenoid from Agyneia bacciformis,A.Juss[J].Acta Crystallogr,2004,60(6):1092-1093.
[3]	Lu C, Bai L, Shen Y. Five unusual natural carbohydrates from Actinosynnema pretiosum[J].Chem Nat Comp,2008,44(5):594-597.
[4]	Bredt DS,Snyder SH.Nitric oxide,a physiological messenger molecule[J].Annu Rev Biochem,1994,63:175-195.
[5]	Kojda G,Kottenberg K.Regulation of basal myocardial function by NO[J].Cardiovasc Res,1999,41(3):514-523.
[6]	Nathan C,Xie Q.Nitric oxide synthases:roles,tolls,and controls[J].Cell,1994,78(6):915-918.
[7]	Wang CH,Wen L,Liu HL,et al.Five natural carbohydrates from the leaves of Sauropus rostratus[J].Carbohydr Res,2013,384(1):99-101.
[8]	Yang K,Wang Z,Brenner T,et al.Sucrose release from agar gels:effects of dissolution order and the network in homogeneity[J].Food Hydrocolloids,2015,43:100-106.
[9]	Kikuchi H,Saito Y,Komiya J,et al.Furanodictine A and B:amino sugar analogues produced by cellular slime mold dictyostelium discoideum showing neuronal differentiation activity[J].J Org Chem,2001,66(21):6982-6987.
[10]	Saulnier MG,Langley DR,Frennesson DB,et al.Novel 3′,6′-anhydro and N12,N13-bridged glycosylated fluoroindolo[2,3-a]carbazoles as topoisomerase I inhibitors.Fluorine as a leaving group from sp³ carbon[J].Org Lett,2005,7(7):1271-1274.
[11]	Shiraiwa K,Yuan S,Fujiyama A,et al.Benzyl benzoate glycoside and 3-deoxy-D-manno-2-octulosonic acid derivatives from Solidago decurrens[J].J Nat Prod,2011,75(1):88-92.
[12]	Fujita K,Yamamura H,Imoto T,et al.Synthesis of 6A,6X-di-O-(p-tosyl)-.gamma.-cyclodextrins and their structural determination through enzymic hydrolysis of 3A,6A;3X,6X-dianhydro-γ-cyclodextrins[J].J Org Chem,1988,53(9):1943.
[13]	Fujita K,Tahara T,Yamamura H,et al.Specific preparation and structure determination of 3A,3C,3E-tri-O-sulfonyl-β-cyclodextrin[J].J Org Chem,1990,55(3):877.
[14]	Jadhav V,Pedersen CM,Bols M.A study of anhydrocellulosesis a cellulose structure with residues in a ¹C₄conformation more prone to hydrolysis[J].Org Biomol Chem,2011,9(21):7525.
[15]	Liu L,Wang CQ,Liu D,et al.Construction of 3,6-anhydrohexosides via intramolecular cyclization of triflates and its application to the synthesis of natural product isolated from leaves of Sauropus rostratus[J].Org Lett,2014,16(19):5004-5007.
[16]	Zhang CX,Wang CQ,Wang ZH,et al.Total synthesis,structural elucidation and anti-inflammatory activity evaluation of 2-deoxy-3,6-anhydro hexofuranoside derivatives isolated from Sauropus rostratus[J].Org Biomol Chem,2016,14(46):10906-10913.