The enantioselective O-allylic alkylation of acetophenone oxime with various Morita-Baylis-Hillman (MBH) carbonates has been accomplished by the catalysis of a commercially available cinchona alkaloid (DHQD)2PHAL. The...The enantioselective O-allylic alkylation of acetophenone oxime with various Morita-Baylis-Hillman (MBH) carbonates has been accomplished by the catalysis of a commercially available cinchona alkaloid (DHQD)2PHAL. The corresponding O-allylic products were obtained in moderate to excellent yields up to 96% ee.展开更多
An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ...An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ up to 30 ： 1） and moderate enantioselectivity （up to 70% ee）.展开更多
An organocatalytic asymmetric branching sequence was realized in the presence of 10 mol% of （DHQD）2AQN, affording the sequential products with three stereocentres, including two quaternary carbon centres, in 47%-79%...An organocatalytic asymmetric branching sequence was realized in the presence of 10 mol% of （DHQD）2AQN, affording the sequential products with three stereocentres, including two quaternary carbon centres, in 47%-79% yields with 85%-99% ee.展开更多
The saccharide-based chiral bifunctional thiourea-phosphines were developed as chiral organocatalysts for the intramolecular Morita-Baylis-Hillman reaction of o^-formyl-enones. With only 2 tool% of thiourea-phosphine ...The saccharide-based chiral bifunctional thiourea-phosphines were developed as chiral organocatalysts for the intramolecular Morita-Baylis-Hillman reaction of o^-formyl-enones. With only 2 tool% of thiourea-phosphine cata- lyst 3c, chiral functionalized cyclohexenes were achieved under mild reaction conditions with excellent yields and enantioselectivities.展开更多
The enantioselective allylic amination of Morita-Baylis-Hillman acetates catalyzed by chiral cyclohexane-based thiourea-phosphine catalysts was investigated. In the presence of 20 mol% rosin-derived thiourea-phosphine...The enantioselective allylic amination of Morita-Baylis-Hillman acetates catalyzed by chiral cyclohexane-based thiourea-phosphine catalysts was investigated. In the presence of 20 mol% rosin-derived thiourea-phosphine 3j, the chiral amines were obtained in up to 88% yield and up to 85% ee.展开更多
A class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita-Baylis-Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose-...A class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita-Baylis-Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose- based phosphinothiourea ld, the allylic alcohols were obtained in up to 96% yield and 83% ee under mild reaction conditions.展开更多
A novel Dendritic Compound (2) of triphenylene- 2,6,10-trione ketal-tri-{2,2-di-[(N-methyl-N-(4-py- ridinyl) amino)methyl]-1,3-propanediol} was conveniently synthesized by aromatization of cyclohexanedione mono-ketal,...A novel Dendritic Compound (2) of triphenylene- 2,6,10-trione ketal-tri-{2,2-di-[(N-methyl-N-(4-py- ridinyl) amino)methyl]-1,3-propanediol} was conveniently synthesized by aromatization of cyclohexanedione mono-ketal, ketal-exchange reaction with 2,2-dibromomethyl-1,3-propane- diol and nuclophilic substitution with N-methy- laminopyridine as nuclophilic reagent. The Mo-rita-Baylis-Hillman reaction of various aryl al-dehydes with methyl vinyl ketone and acryloni-trile in (DMF/cyclohexane, 1/1, v/v) has been investigated by using Dendritic Compound (2) as catalyst. The corresponding Morita-Baylis- Hillman adducts was obtained in good yields by using the recycled and reactivated dendritic catalyst.展开更多
A convenient method for Morita-Baylis-Hillman reaction of arylaldehydes with methyl acrylate has been developed by using fluorous-tag organocatalyst 1-[4-（perfluorooctyl）phenyl]-3-phenylthiourea and DABCO at room te...A convenient method for Morita-Baylis-Hillman reaction of arylaldehydes with methyl acrylate has been developed by using fluorous-tag organocatalyst 1-[4-（perfluorooctyl）phenyl]-3-phenylthiourea and DABCO at room temperature. The fluorous organocatalyst could be recovered from the reaction mixture by fluorous solid-phase extraction （F-SPE） with excellent purity for direct reuse.展开更多
We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of ...We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.展开更多
A simple primary-tertiary diamine has been explored as a novel catalyst for the Morita-Baylis-Hillman reaction of MVK and aryl aldehydes, and moderate to good chemical yields were obtained. Detailed mechanism study in...A simple primary-tertiary diamine has been explored as a novel catalyst for the Morita-Baylis-Hillman reaction of MVK and aryl aldehydes, and moderate to good chemical yields were obtained. Detailed mechanism study indicated that the diamine acted as a bifunctional cooperation catalyst via a bicyclic enamino-quaternary ammonium intermediate.展开更多
FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman （MBH） alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetyl...FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman （MBH） alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetylene-substituted products in good yields.展开更多
The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The...The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).展开更多
Summary of main observation and conclusion 3-Olefinic oxindoles can undergo interrupted Morita-Baylis-Hillman reaction with formaldehyde. Apart from the previous reported dephosphoration to access reductive aldol-type...Summary of main observation and conclusion 3-Olefinic oxindoles can undergo interrupted Morita-Baylis-Hillman reaction with formaldehyde. Apart from the previous reported dephosphoration to access reductive aldol-type products, here we uncovered that completely different pathways were followed by tuning the substitutions of 3-olefinic oxin doles. In com bin ation with formalin, an unexpected domino phosphorus-ylide formation, aldol-type addition, hemeacetal formation and O-substitution process was observed to produce 1,3-dioxolane derivatives. Moreover, a switchable sequence to produce formate derivatives via a key hydride transfer process was furnished by simply replacing formalin with paraformaldehyde. Density functional theory calculations were conducted to well elucidate the catalytic reaction mechanism.展开更多
基金Supported by the National Natural Science Foundation of China (Grant No. 20772084)
文摘The enantioselective O-allylic alkylation of acetophenone oxime with various Morita-Baylis-Hillman (MBH) carbonates has been accomplished by the catalysis of a commercially available cinchona alkaloid (DHQD)2PHAL. The corresponding O-allylic products were obtained in moderate to excellent yields up to 96% ee.
文摘An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ up to 30 ： 1） and moderate enantioselectivity （up to 70% ee）.
基金Acknowledgement This work was supported financially by the National Natural Science Foundation of China （Nos. 20972110 and 20902067）.
文摘An organocatalytic asymmetric branching sequence was realized in the presence of 10 mol% of （DHQD）2AQN, affording the sequential products with three stereocentres, including two quaternary carbon centres, in 47%-79% yields with 85%-99% ee.
文摘The saccharide-based chiral bifunctional thiourea-phosphines were developed as chiral organocatalysts for the intramolecular Morita-Baylis-Hillman reaction of o^-formyl-enones. With only 2 tool% of thiourea-phosphine cata- lyst 3c, chiral functionalized cyclohexenes were achieved under mild reaction conditions with excellent yields and enantioselectivities.
基金We are grateful for the financial support from the National Natural Science Foundation of China （Nos. 21242007, 21102043）, Science and Technology Com- mission of Shanghai Municipality （No. 15ZR1409200）, and the Fundamental Research Funds for the Central Universities.
文摘The enantioselective allylic amination of Morita-Baylis-Hillman acetates catalyzed by chiral cyclohexane-based thiourea-phosphine catalysts was investigated. In the presence of 20 mol% rosin-derived thiourea-phosphine 3j, the chiral amines were obtained in up to 88% yield and up to 85% ee.
基金Acknowledgement We are grateful for the financial support from the National Natural Science Foundation of China （No. 20772029）, the Program for New Century Excellent Talents in University （No. NCET-07-0286） and the Fundamental Research Funds for the Central Universities.
文摘A class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita-Baylis-Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose- based phosphinothiourea ld, the allylic alcohols were obtained in up to 96% yield and 83% ee under mild reaction conditions.
文摘A novel Dendritic Compound (2) of triphenylene- 2,6,10-trione ketal-tri-{2,2-di-[(N-methyl-N-(4-py- ridinyl) amino)methyl]-1,3-propanediol} was conveniently synthesized by aromatization of cyclohexanedione mono-ketal, ketal-exchange reaction with 2,2-dibromomethyl-1,3-propane- diol and nuclophilic substitution with N-methy- laminopyridine as nuclophilic reagent. The Mo-rita-Baylis-Hillman reaction of various aryl al-dehydes with methyl vinyl ketone and acryloni-trile in (DMF/cyclohexane, 1/1, v/v) has been investigated by using Dendritic Compound (2) as catalyst. The corresponding Morita-Baylis- Hillman adducts was obtained in good yields by using the recycled and reactivated dendritic catalyst.
基金the project of"Excellence Initiative"and"Zijin Star"in NJUST,"Doctoral Fund of Ministry of Education of China"(No.200802881024)"National Natural Science Foundation of China"(No.20902047) for financial support
文摘A convenient method for Morita-Baylis-Hillman reaction of arylaldehydes with methyl acrylate has been developed by using fluorous-tag organocatalyst 1-[4-（perfluorooctyl）phenyl]-3-phenylthiourea and DABCO at room temperature. The fluorous organocatalyst could be recovered from the reaction mixture by fluorous solid-phase extraction （F-SPE） with excellent purity for direct reuse.
文摘We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama＇s catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20421202, 20632060 and 20702052)Ministry of Science and Technology of China (Grant No. 2008CB617501 & 2009ZX09501-018), and the Chinese Academy of Sciences
文摘A simple primary-tertiary diamine has been explored as a novel catalyst for the Morita-Baylis-Hillman reaction of MVK and aryl aldehydes, and moderate to good chemical yields were obtained. Detailed mechanism study indicated that the diamine acted as a bifunctional cooperation catalyst via a bicyclic enamino-quaternary ammonium intermediate.
基金Project supported by the National Natural Science Foundation of China, Ministry of Science and Technology （973 Program, No. 2011CB808600） and the Chinese Academy of Sciences.
文摘FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman （MBH） alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetylene-substituted products in good yields.
基金financially Supported by the National Natural Science Foundation of China (20772084)
文摘The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).
文摘Summary of main observation and conclusion 3-Olefinic oxindoles can undergo interrupted Morita-Baylis-Hillman reaction with formaldehyde. Apart from the previous reported dephosphoration to access reductive aldol-type products, here we uncovered that completely different pathways were followed by tuning the substitutions of 3-olefinic oxin doles. In com bin ation with formalin, an unexpected domino phosphorus-ylide formation, aldol-type addition, hemeacetal formation and O-substitution process was observed to produce 1,3-dioxolane derivatives. Moreover, a switchable sequence to produce formate derivatives via a key hydride transfer process was furnished by simply replacing formalin with paraformaldehyde. Density functional theory calculations were conducted to well elucidate the catalytic reaction mechanism.
