Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both...Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates,facilitating the synthesis of mono-,di-,tri-,and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions.Mechanistic investigations indicate that the in situ generated Ni(Ⅰ)complex might serve as the active species to react with propargylic esters,forming the allenyl-Ni(Ⅰ)complex under electroreductive conditions.A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ)complex on CO_(2) is likely involved in the formation of the desired 2,3-allenoic acids.展开更多
Water-promoted sulfonylation of propargyl esters leading to highly regioselective and stereoselective formation of （Z）-β-sulfonyl enoates in excellent yields, by a simple, mild, rapid and environmentally benign rea...Water-promoted sulfonylation of propargyl esters leading to highly regioselective and stereoselective formation of （Z）-β-sulfonyl enoates in excellent yields, by a simple, mild, rapid and environmentally benign reaction proce- dure is reported.展开更多
带不同取代基团的吲哚丙炔酯化合物在氯化铂的催化下,用甲苯作溶剂,反应温度为120℃,自身发生环化反应生成咔唑类化合物。其结构用质谱、1 H NMR、13 C NMR等手段进行了表征。通过研究反应机理和影响反应的因素发现,在吲哚N上连的不同...带不同取代基团的吲哚丙炔酯化合物在氯化铂的催化下,用甲苯作溶剂,反应温度为120℃,自身发生环化反应生成咔唑类化合物。其结构用质谱、1 H NMR、13 C NMR等手段进行了表征。通过研究反应机理和影响反应的因素发现,在吲哚N上连的不同保护基对反应影响较大,保护基的吸电子性越强时,成环反应更容易进行。展开更多
The stereochemical synthesis of highly substituted Danishefsky-type dienes remains unsolved in organic chemistry.We describe a simple and efficient approach for the stereoselective synthesis of Danishefsky-type trisub...The stereochemical synthesis of highly substituted Danishefsky-type dienes remains unsolved in organic chemistry.We describe a simple and efficient approach for the stereoselective synthesis of Danishefsky-type trisubstituted dienes from readily available propargylic esters via Pd-catalyzed dienylation reaction through the key intermediate metallacyclobutene in a regio-,chemo-and stereoselective fashion.This method facilitates a broad range of challenging trisubstituted dienes with a high level of stereocontrol.展开更多
1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in s...1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry due to conjugated repeating C=C units. Accordingly, various strategies to access substituted 1,3-dienes in a stereoselective manner have been developed. However, chemo-, regio-and stereoselective synthesis of highly substituted 1,3-dienes still remains elusive and challenging. Readily available propargylic esters have emerged as an appealing class of synthetic intermediates for accessing functionalized 1,3-dienes, especially challenging tri-or tetrasubstituted variants, via transition-metal catalysis, including electrophilic metal and redox neutral catalysis. This review, for the first time, systematically highlights recent advances in transitionmetal catalyzed synthesis of substituted 1,3-dienes from propargylic esters, discusses the mechanisms and synthetic utilities, and gives the remaining challenges and potential opportunities in this field.展开更多
A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substit...A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substitution cascade.Unlike the known polyene-type cyclization strategies for the construction of abietane-type diterpene skeletons,propargylic ester groups were used for the cyclization process,which can readily lead to the key skeleton with C2 and C3 functionalization.As a demonstration of the potential application of this tandem reaction,a collective total synthesis of(±)-2-ketoferruginol,(±)-fleuryinol B,(±)-salviol,(±)-2β-acetoxyferruginol,and(±)-2β-acetoxysugiyl methyl ether was achieved.Among these molecules,(±)-fleuryinol B and(±)-2β-acetoxyferruginol were synthesized for the first time.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22171090,21871090)National Key Research and Development Program of China(No.2020YFA0710200)+1 种基金the Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD37)the Fundamental Research Funds for the Central Universities are highly appreciated。
文摘Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates,facilitating the synthesis of mono-,di-,tri-,and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions.Mechanistic investigations indicate that the in situ generated Ni(Ⅰ)complex might serve as the active species to react with propargylic esters,forming the allenyl-Ni(Ⅰ)complex under electroreductive conditions.A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ)complex on CO_(2) is likely involved in the formation of the desired 2,3-allenoic acids.
文摘Water-promoted sulfonylation of propargyl esters leading to highly regioselective and stereoselective formation of （Z）-β-sulfonyl enoates in excellent yields, by a simple, mild, rapid and environmentally benign reaction proce- dure is reported.
文摘带不同取代基团的吲哚丙炔酯化合物在氯化铂的催化下,用甲苯作溶剂,反应温度为120℃,自身发生环化反应生成咔唑类化合物。其结构用质谱、1 H NMR、13 C NMR等手段进行了表征。通过研究反应机理和影响反应的因素发现,在吲哚N上连的不同保护基对反应影响较大,保护基的吸电子性越强时,成环反应更容易进行。
基金funding from the National Natural Science Foundation of China(Nos.22071111 and 22371125)Jiangsu Specially Appointed Professor Plan,and Postgraduate Research&Practice Innovation Program of Jiangsu Province of China(No.KYCX23_1683).
文摘The stereochemical synthesis of highly substituted Danishefsky-type dienes remains unsolved in organic chemistry.We describe a simple and efficient approach for the stereoselective synthesis of Danishefsky-type trisubstituted dienes from readily available propargylic esters via Pd-catalyzed dienylation reaction through the key intermediate metallacyclobutene in a regio-,chemo-and stereoselective fashion.This method facilitates a broad range of challenging trisubstituted dienes with a high level of stereocontrol.
基金supported by the National Natural Science Foundation of China (22071111)the Jiangsu Specially Appointed Professor Plan+1 种基金the Natural Science Foundation of Jiangsu Province(BK20201368, BK20220409)the Postgraduate Research&Practice Innovation Program of Jiangsu Province (KYCX23_1683)。
文摘1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry due to conjugated repeating C=C units. Accordingly, various strategies to access substituted 1,3-dienes in a stereoselective manner have been developed. However, chemo-, regio-and stereoselective synthesis of highly substituted 1,3-dienes still remains elusive and challenging. Readily available propargylic esters have emerged as an appealing class of synthetic intermediates for accessing functionalized 1,3-dienes, especially challenging tri-or tetrasubstituted variants, via transition-metal catalysis, including electrophilic metal and redox neutral catalysis. This review, for the first time, systematically highlights recent advances in transitionmetal catalyzed synthesis of substituted 1,3-dienes from propargylic esters, discusses the mechanisms and synthetic utilities, and gives the remaining challenges and potential opportunities in this field.
基金supported by the National Natural Science Foundation of China(nos.21472077 and 21772071)Department of Education of Guangdong Province(nos.2017KTSCX185,2017KSYS010,2016KCXTD005,and 2019KZDXM035).
文摘A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substitution cascade.Unlike the known polyene-type cyclization strategies for the construction of abietane-type diterpene skeletons,propargylic ester groups were used for the cyclization process,which can readily lead to the key skeleton with C2 and C3 functionalization.As a demonstration of the potential application of this tandem reaction,a collective total synthesis of(±)-2-ketoferruginol,(±)-fleuryinol B,(±)-salviol,(±)-2β-acetoxyferruginol,and(±)-2β-acetoxysugiyl methyl ether was achieved.Among these molecules,(±)-fleuryinol B and(±)-2β-acetoxyferruginol were synthesized for the first time.
