Continuous research on Cephalotaxus plants has ultimately led to the US food and drug administration (FDA) ap-provalof homoharringtonine in 2012 for the treatment of chronic myeloid leukemia. Additionally, another imp...Continuous research on Cephalotaxus plants has ultimately led to the US food and drug administration (FDA) ap-provalof homoharringtonine in 2012 for the treatment of chronic myeloid leukemia. Additionally, another important class of natural products from Cephalotaxus plants is cephalotane diterpenoids. Since the discovery of the first member, harring-tonolide,in 1978, cephalotane diterpenoids have garnered significant attention from the scientific community due to their re-markableanti-cancer activity. The unique structural features of cephalotane diterpenoids, a 7/6/5/6-fused tetracyclic carbon skeleton and a bridged lactone, make them ideal targets for synthetic chemists. Successfully synthesizing these complex diterpenoids is of great importance for the discovery and development of anti-tumor drugs. To date, ten research groups have completed the total synthesis of 24 cephalotane diterpenoids. The latest progress in the total synthesis of cephalotane diterpe-noidsis reviewed, showcasing the importance of these innovative synthetic strategies in the efficient synthesis of complex natural products and their potential significance in advancing the field of drug discovery.展开更多
A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional poly...A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.展开更多
The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aroma...The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10.The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction.Dysideanone G(6)was easily prepared on a gram-scale and dysideanones A,E,and F(1,4,and 5)were divergently transformed from dysideanone G(6)in one or two steps.展开更多
The authors regret that in the original article,the structure of(–)-swainsonine(1)in Graphical abstract,Fig.1,Schemes 1 and 3 was incorrect.The correct structure is shown here.
The first total synthesis of(+)-taberdicatine B and(+)-tabernabovine B has been accomplished in 10steps with 26.9% overall yield and 15 steps with 7.3% overall yield,respectively.The prominent features of this efficie...The first total synthesis of(+)-taberdicatine B and(+)-tabernabovine B has been accomplished in 10steps with 26.9% overall yield and 15 steps with 7.3% overall yield,respectively.The prominent features of this efficient synthetic strategy include the following:(1)(+)-Taberdicatine B and(+)-tabernabovine B were accessed from common advanced intermediates by varying the substituents;(2) A one-pot asymmetric bromocyclization/hydrolysis was explored to assemble HPI skeleton;(3) Dieckmann condensation to form β-keto ester for the assembly of seven-membered ring;(4) An ester reduction/amide semireduction/cyclization sequence was applied to form the cage-like framework.展开更多
Aim To design a practical synthetic route of anisodine. Methods Starting from3α-hydroxy-6β-acetyltropine, anisodine was synthesized in 11 steps. Result Anisodine wasobtainded with an overall yield of 2.6 % . Conclus...Aim To design a practical synthetic route of anisodine. Methods Starting from3α-hydroxy-6β-acetyltropine, anisodine was synthesized in 11 steps. Result Anisodine wasobtainded with an overall yield of 2.6 % . Conclusion Total synthetic route of anisodine wasachieved which may afford a possible route for commercial preparation of anisodine.展开更多
The total synthesis of （±）-abyssinoflavanone V was first achieved through C-prenylation, selective protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap 4-h...The total synthesis of （±）-abyssinoflavanone V was first achieved through C-prenylation, selective protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap 4-hydroxybenzaldehyde and 2,4,6- trihydroxyacetophenone, with total yield 24%. All structures of new compounds were confirmed by IR, 1^H NMR and MS.展开更多
The total synthesis of （＋）-8-（3-methylbut-2-enyl）-2-phenyl-2,3-dihydrochromen-4-one and （±）-2-（4-hydroxyphenyl）-8-（3- methylbut-2-enyl）-2,3-dihydrochromen-4-one was first achieved through C-prenylation...The total synthesis of （＋）-8-（3-methylbut-2-enyl）-2-phenyl-2,3-dihydrochromen-4-one and （±）-2-（4-hydroxyphenyl）-8-（3- methylbut-2-enyl）-2,3-dihydrochromen-4-one was first achieved through C-prenylation, protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap benzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxyace- tophenone, with total yield of 20 and 16.3%. All structures of new compounds were confirmed by IR, 1H NMR and MS. 2009 Jin Hui Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
The total synthesis of a hydrated aurone derivative, 2-benzyl-4-methoxy-2,6-dihydroxybenzofuran-3（2H）-one, has been achieved for the first time with 2.4% overall yield. Using phloroglucinol as the starting material,...The total synthesis of a hydrated aurone derivative, 2-benzyl-4-methoxy-2,6-dihydroxybenzofuran-3（2H）-one, has been achieved for the first time with 2.4% overall yield. Using phloroglucinol as the starting material, the key steps included Friedel-Crafts acylation, Williamson synthesis, hydrogenolysis, aldol condensation, enolization and Rubottom oxidation.展开更多
Mycothiol （MSH） is the major low molecular weight thiol in most actinomycetes. Chemical synthesis of MSH is of value for enzymology and inhibitor screening assays, but is hampered by difficulties in large scale sysn...Mycothiol （MSH） is the major low molecular weight thiol in most actinomycetes. Chemical synthesis of MSH is of value for enzymology and inhibitor screening assays, but is hampered by difficulties in large scale sysnthesis. We achieved the total synthesis of MSH by linking 2-camphanoyl-3,4,5,6-tetra-O-benzyl-D-rnyo-inositol （D-1） and 2-deoxy-2-azido-3,4,6-tri-O-benzyl- 1-p-toluene-thio-o-glucoside （2） first, followed by coupling with N-Boc-S-acetyl-L-cysteine （3）. This route of synthesis allowed the efficient and convenient synthesis of mycothiol on a large scale.展开更多
Attempts to collective synthesis of the monoterpene indole alkaloids, isolated from Nauclea species, were examined by using asymmetric conjugate addition with Evans＇chiral auxiliary as key step. However, only the H-1...Attempts to collective synthesis of the monoterpene indole alkaloids, isolated from Nauclea species, were examined by using asymmetric conjugate addition with Evans＇chiral auxiliary as key step. However, only the H-15 and H-3 cis product 13 was obtained, which enabled us to achieve the asymmetric total synthesis of 3-epi-naucleamide A. The results indicate that this synthetic route can be applied in the synthesis of vincosamide.展开更多
All stereoisomers of asperphenamate 1a and patriscabratine 2a were achieved with a high yield,and total synthesis of 2a is firstly described here.The absolute configuration of patriscabratine was determined as(S,S).Th...All stereoisomers of asperphenamate 1a and patriscabratine 2a were achieved with a high yield,and total synthesis of 2a is firstly described here.The absolute configuration of patriscabratine was determined as(S,S).The compounds 1a-d and 2a-d have been tested by MTT assay in T47D,MDA-MB231,HL60,Hela and SGC-7901 cell lines in vitro.Among them,the(R,S) stereoisomer shows the strongest anticancer effects,while the(S,R) shows the weakest one.展开更多
Protein tyrosine phosphatase 1B （PTP1B） plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-（2,3-dibromo-4,5-dihydroxyphe...Protein tyrosine phosphatase 1B （PTP1B） plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-（2,3-dibromo-4,5-dihydroxyphenyl）-methane 7 was first reported as a natural bromophenol with significant inhibition against PTP1B which was isolated from red algae Rhodomela conrervoides. Intrigued by its astonishing activity （IC50 = 2.4 μmol/L）, compound 7 was synthesized with the overall yield of 24% and evaluated for its PTPIB inhibitory activity compared with natural compound.展开更多
A new isochroman-4-one, 7,8-dihydroxy-3-methylisochroman-4-one was isolated from water soluble fraction of Musa sapientum L. Its structure was determined by spectroscopic evidences and its total synthesis has also bee...A new isochroman-4-one, 7,8-dihydroxy-3-methylisochroman-4-one was isolated from water soluble fraction of Musa sapientum L. Its structure was determined by spectroscopic evidences and its total synthesis has also been reported. The compound showed potent antihypertensive activity.展开更多
A facile approach for the first total synthesis of two naturally occurring geranylated flavonoids,（±）-puyanin 1 and（±）-4＇-O- methylbonannione 2 has been obtained with total yield 27%and 21%,respectively...A facile approach for the first total synthesis of two naturally occurring geranylated flavonoids,（±）-puyanin 1 and（±）-4＇-O- methylbonannione 2 has been obtained with total yield 27%and 21%,respectively.The key steps were regioselective cyclization of geranylated trihydroxychalcone and regioselective geranylation of 2,4,6-trihydroxyacetophenone.展开更多
The first synthesis of squarnosamide,a new compound isolated from Annona squamosa, was achieved in seven steps.The over all yield was 14%.The compound was identified by^1 H,^(13)C NMR and MS.
Kadsurenin M (7s, 8s- 3, 4, 3'- trimethoxy- 7'- o\o- nor-8', 9'-7. O, 4' - 8, 5'-neolingan)(1), a benzofuranoid neolignan isolated tyom the aerial part of Piper Kadsura (Choisy) Ohwi,was synthe...Kadsurenin M (7s, 8s- 3, 4, 3'- trimethoxy- 7'- o\o- nor-8', 9'-7. O, 4' - 8, 5'-neolingan)(1), a benzofuranoid neolignan isolated tyom the aerial part of Piper Kadsura (Choisy) Ohwi,was synthesized in 6 steps from vanillin via a key intermediate 3,4- dimethoxycinnamyl (2'-methoxy- 4'- formyl)phenyl ether (7). The overall yield is 15%.展开更多
A naturally occurring nucleoside disulfide, 9-（51-deoxy-5t-thio-β-D-xylofuranosyl）adenine disulfide, was first synthesized from o-xylose over 7 steps in 20% overall yield. The key step involved Vorbri.iggen glycosy...A naturally occurring nucleoside disulfide, 9-（51-deoxy-5t-thio-β-D-xylofuranosyl）adenine disulfide, was first synthesized from o-xylose over 7 steps in 20% overall yield. The key step involved Vorbri.iggen glycosylation of silylated N6-benzoyladenine with xylose diacetate moiety.展开更多
Anti-HIV agent (±)-calanolide A has been synthesized by a four-step approach startingfrom phloroglucinol, including the Pechmann reaction, Friedel-Crafts acylation, cyclization,chromenylation and Luche reduction.
We report the first total synthesis of four possible absolute configurations and four other regional isomers of a naturally occurring alkaloid crotonine,which was isolated from Croton tiglium L.(Euphoriaceae)without e...We report the first total synthesis of four possible absolute configurations and four other regional isomers of a naturally occurring alkaloid crotonine,which was isolated from Croton tiglium L.(Euphoriaceae)without elucidation of its absolute configuration.The concise five-step route with a chirally poor and regioselective strategy starting from monosaccharides was established,and the absolute structure of the natural crotonine was determined by comparison of the NMR spectra and optical rotations of the synthetic products.展开更多
文摘Continuous research on Cephalotaxus plants has ultimately led to the US food and drug administration (FDA) ap-provalof homoharringtonine in 2012 for the treatment of chronic myeloid leukemia. Additionally, another important class of natural products from Cephalotaxus plants is cephalotane diterpenoids. Since the discovery of the first member, harring-tonolide,in 1978, cephalotane diterpenoids have garnered significant attention from the scientific community due to their re-markableanti-cancer activity. The unique structural features of cephalotane diterpenoids, a 7/6/5/6-fused tetracyclic carbon skeleton and a bridged lactone, make them ideal targets for synthetic chemists. Successfully synthesizing these complex diterpenoids is of great importance for the discovery and development of anti-tumor drugs. To date, ten research groups have completed the total synthesis of 24 cephalotane diterpenoids. The latest progress in the total synthesis of cephalotane diterpe-noidsis reviewed, showcasing the importance of these innovative synthetic strategies in the efficient synthesis of complex natural products and their potential significance in advancing the field of drug discovery.
基金the National Natural Science Foundation of China(No.22471224)。
文摘A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.
基金Financial support for this work was provided by the National Natural Science Foundation of China(Nos.22171146,21971121,and 22188101)the Fundamental Research Funds for the Central Universities,Nankai University(No.63231199)the State Key Laboratory of Medicinal Chemical Biology。
文摘The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10.The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction.Dysideanone G(6)was easily prepared on a gram-scale and dysideanones A,E,and F(1,4,and 5)were divergently transformed from dysideanone G(6)in one or two steps.
文摘The authors regret that in the original article,the structure of(–)-swainsonine(1)in Graphical abstract,Fig.1,Schemes 1 and 3 was incorrect.The correct structure is shown here.
基金the Qingdao Marine Science and Technology Center(No.2022QNLM030003-2)the Fundamental Research Funds for the Central Universities,Taishan Scholar Program of Shandong Province(No.tsqn202103152)National Natural Science Foundation of China(No.22171251) for financial support。
文摘The first total synthesis of(+)-taberdicatine B and(+)-tabernabovine B has been accomplished in 10steps with 26.9% overall yield and 15 steps with 7.3% overall yield,respectively.The prominent features of this efficient synthetic strategy include the following:(1)(+)-Taberdicatine B and(+)-tabernabovine B were accessed from common advanced intermediates by varying the substituents;(2) A one-pot asymmetric bromocyclization/hydrolysis was explored to assemble HPI skeleton;(3) Dieckmann condensation to form β-keto ester for the assembly of seven-membered ring;(4) An ester reduction/amide semireduction/cyclization sequence was applied to form the cage-like framework.
文摘Aim To design a practical synthetic route of anisodine. Methods Starting from3α-hydroxy-6β-acetyltropine, anisodine was synthesized in 11 steps. Result Anisodine wasobtainded with an overall yield of 2.6 % . Conclusion Total synthetic route of anisodine wasachieved which may afford a possible route for commercial preparation of anisodine.
基金We thank the National Natural Science Foundation （No. 20562010）；Ministry of National Education （No.203143）for financial support.
文摘The total synthesis of （±）-abyssinoflavanone V was first achieved through C-prenylation, selective protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap 4-hydroxybenzaldehyde and 2,4,6- trihydroxyacetophenone, with total yield 24%. All structures of new compounds were confirmed by IR, 1^H NMR and MS.
基金the National Natural Science Foundation(No.20562010)Ministry of National Education(No.203143)for financial support
文摘The total synthesis of （＋）-8-（3-methylbut-2-enyl）-2-phenyl-2,3-dihydrochromen-4-one and （±）-2-（4-hydroxyphenyl）-8-（3- methylbut-2-enyl）-2,3-dihydrochromen-4-one was first achieved through C-prenylation, protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap benzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxyace- tophenone, with total yield of 20 and 16.3%. All structures of new compounds were confirmed by IR, 1H NMR and MS. 2009 Jin Hui Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘The total synthesis of a hydrated aurone derivative, 2-benzyl-4-methoxy-2,6-dihydroxybenzofuran-3（2H）-one, has been achieved for the first time with 2.4% overall yield. Using phloroglucinol as the starting material, the key steps included Friedel-Crafts acylation, Williamson synthesis, hydrogenolysis, aldol condensation, enolization and Rubottom oxidation.
基金National Natural Science Foundation of China(NSFC,Grant No.91213303)
文摘Mycothiol （MSH） is the major low molecular weight thiol in most actinomycetes. Chemical synthesis of MSH is of value for enzymology and inhibitor screening assays, but is hampered by difficulties in large scale sysnthesis. We achieved the total synthesis of MSH by linking 2-camphanoyl-3,4,5,6-tetra-O-benzyl-D-rnyo-inositol （D-1） and 2-deoxy-2-azido-3,4,6-tri-O-benzyl- 1-p-toluene-thio-o-glucoside （2） first, followed by coupling with N-Boc-S-acetyl-L-cysteine （3）. This route of synthesis allowed the efficient and convenient synthesis of mycothiol on a large scale.
基金National Natural Science Foundation of China(Grant No.21290183and 21572008)
文摘Attempts to collective synthesis of the monoterpene indole alkaloids, isolated from Nauclea species, were examined by using asymmetric conjugate addition with Evans＇chiral auxiliary as key step. However, only the H-15 and H-3 cis product 13 was obtained, which enabled us to achieve the asymmetric total synthesis of 3-epi-naucleamide A. The results indicate that this synthetic route can be applied in the synthesis of vincosamide.
文摘All stereoisomers of asperphenamate 1a and patriscabratine 2a were achieved with a high yield,and total synthesis of 2a is firstly described here.The absolute configuration of patriscabratine was determined as(S,S).The compounds 1a-d and 2a-d have been tested by MTT assay in T47D,MDA-MB231,HL60,Hela and SGC-7901 cell lines in vitro.Among them,the(R,S) stereoisomer shows the strongest anticancer effects,while the(S,R) shows the weakest one.
基金the National Center for Drug Screening (Shanghai,PR China) for supplying data on PTP1B inhibitory activities of compoundssupported by the National 863 projects (Nos.2007AA09Z410 and 2007AA091604).
文摘Protein tyrosine phosphatase 1B （PTP1B） plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-（2,3-dibromo-4,5-dihydroxyphenyl）-methane 7 was first reported as a natural bromophenol with significant inhibition against PTP1B which was isolated from red algae Rhodomela conrervoides. Intrigued by its astonishing activity （IC50 = 2.4 μmol/L）, compound 7 was synthesized with the overall yield of 24% and evaluated for its PTPIB inhibitory activity compared with natural compound.
文摘A new isochroman-4-one, 7,8-dihydroxy-3-methylisochroman-4-one was isolated from water soluble fraction of Musa sapientum L. Its structure was determined by spectroscopic evidences and its total synthesis has also been reported. The compound showed potent antihypertensive activity.
基金financially supported by the National Natural Science Foundation(Nos.20562010,20962016)Ningxia Natural Science Foundation,Program for New Century Excellent Talents in University(No.NCET-09-0860)the National Basic Research Program 973 of China(No.2010CB534916)
文摘A facile approach for the first total synthesis of two naturally occurring geranylated flavonoids,（±）-puyanin 1 and（±）-4＇-O- methylbonannione 2 has been obtained with total yield 27%and 21%,respectively.The key steps were regioselective cyclization of geranylated trihydroxychalcone and regioselective geranylation of 2,4,6-trihydroxyacetophenone.
文摘The first synthesis of squarnosamide,a new compound isolated from Annona squamosa, was achieved in seven steps.The over all yield was 14%.The compound was identified by^1 H,^(13)C NMR and MS.
文摘Kadsurenin M (7s, 8s- 3, 4, 3'- trimethoxy- 7'- o\o- nor-8', 9'-7. O, 4' - 8, 5'-neolingan)(1), a benzofuranoid neolignan isolated tyom the aerial part of Piper Kadsura (Choisy) Ohwi,was synthesized in 6 steps from vanillin via a key intermediate 3,4- dimethoxycinnamyl (2'-methoxy- 4'- formyl)phenyl ether (7). The overall yield is 15%.
基金NSFC(Nos.20962009 and 21062006)NCET(No.11-1000)+1 种基金the Training Project of Jiangxi Youth Scientists,Education Department of Jiangxi Province(No.GJJ 11223)Bureau of Science & Technology of Nanchang City for financial support
文摘A naturally occurring nucleoside disulfide, 9-（51-deoxy-5t-thio-β-D-xylofuranosyl）adenine disulfide, was first synthesized from o-xylose over 7 steps in 20% overall yield. The key step involved Vorbri.iggen glycosylation of silylated N6-benzoyladenine with xylose diacetate moiety.
文摘Anti-HIV agent (±)-calanolide A has been synthesized by a four-step approach startingfrom phloroglucinol, including the Pechmann reaction, Friedel-Crafts acylation, cyclization,chromenylation and Luche reduction.
基金This work was supported financially and inspired scientifically by Prof.Yongxian Cheng of State Key Laboratory of Phytochemistry and Plant Resources in West China,Kunming Institute of Botany,Chinese Academy of Sciences,and Prof.Baomin Fan of Key Laboratory of Chemistry in Ethnic Medicinal Resources,State Ethnic Affairs Commission&Ministry of Education,Yunnan University of Nationalities.
文摘We report the first total synthesis of four possible absolute configurations and four other regional isomers of a naturally occurring alkaloid crotonine,which was isolated from Croton tiglium L.(Euphoriaceae)without elucidation of its absolute configuration.The concise five-step route with a chirally poor and regioselective strategy starting from monosaccharides was established,and the absolute structure of the natural crotonine was determined by comparison of the NMR spectra and optical rotations of the synthetic products.
