A series of optically active N-protected 1,2-amino alcohols were synthesized via the reduction of the corresponding a-aminoketones starting from the readily available L-amino acids.
Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally di...Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.展开更多
A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction co...A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction conditions.The reaction has a wide substrate scope and operational simplicity.Mechanistic studies suggest that1,2‐carbon migration is induced by regioselective nitrogen‐centered radical addition to the alkene unit.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived β-amino alcohols were synthesized from L-DOPA in good yields. The structures of the target compounds were confirmed by ^1H NMR, ^13C NMR and MS.
Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived G-amino alcohols were synthesized from commercially available LDOPA. These ligands were evaluated in the asymmetric addition of diethylzinc to benzaldehydes and s...Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived G-amino alcohols were synthesized from commercially available LDOPA. These ligands were evaluated in the asymmetric addition of diethylzinc to benzaldehydes and showed different catalytic activities （up to 86% ee）. The solvent played an important role in the enantioselective process. The transition state models were proposed to explain the reversion of the product configuration.展开更多
A highly effective,new chiral 1,2,3,4-tetrahydroisoquinoline catalyst 1 for the diethylzinc addition to aryl aldehydes has been investigated.Using 10 mol%of this chiral catalyst,secondary alcohols can be obtained in u...A highly effective,new chiral 1,2,3,4-tetrahydroisoquinoline catalyst 1 for the diethylzinc addition to aryl aldehydes has been investigated.Using 10 mol%of this chiral catalyst,secondary alcohols can be obtained in up to 87%yield and 99.5%ee under mild conditions.展开更多
The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expect...The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the central C=N double bond. It crystallizes in orthorhombic, space group P2dc with a = 7.632（1）, b = 7.816（1）, c = 28.082（5） A,β = 96.18（1）°, V= 1665.48（51） A^3, Z= 4, Dc = 1.341 g/cm^3, F（000） = 704,μ = 0.094 mm^-1, the final R = 0.0448 and wR = 0.1058. Of the total 3748 collections, 3105 were unique. In the molecule there exist two different planes of pyrazoline and C（11）-C（16） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0.03 A） with the dihedral angle between them of 9.8%.展开更多
The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expect...The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the C=N double bond. It crystallizes in the monoclinic system, space group P2 1/c with a = 11.150（3）, b = 9.906（3）, c = 13.624（4） A, β = 106.360（4）°, V= 1443.9（7） ,A^3, Z = 4, Dc = 1.294 g/cm^3, F（000） = 592,μ（MoKa） = 0.088 mm ^-1, R = 0.0577 and wR = 0.1214. Of the 5766 total reflections, 2540 were unique. In the molecule there exist two different planes of pyrazoline and O（2）-C（10） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0026 A） with the dihedral angle between them of 6.3°.展开更多
采用化学共沉淀方法制备了铜氧化物催化剂FAH-1。在30 m L绝热微型固定床反应器上,研究了催化剂催化糠醇加氢制备1,2-戊二醇的性能,并对相关工艺条件进行了考察。实验结果表明:FAH-1催化剂表现出良好的糠醇加氢活性和选择性,在反应温度...采用化学共沉淀方法制备了铜氧化物催化剂FAH-1。在30 m L绝热微型固定床反应器上,研究了催化剂催化糠醇加氢制备1,2-戊二醇的性能,并对相关工艺条件进行了考察。实验结果表明:FAH-1催化剂表现出良好的糠醇加氢活性和选择性,在反应温度为160℃、反应压力为6 MPa、液时体积空速为0.3 h-1、氢油体积比为10 000∶1条件下,糠醇加氢反应的转化率和选择性分别为91.80%和41.52%,1,2-戊二醇单程收率达到38.12%,1 000 h长周期评价催化剂性能稳定。制得的1,2-戊二醇样品纯度高、质量好,满足后续加工对1,2-戊二醇的质量要求。反应过程采用固定床反应器,具有较好的工业化前景。展开更多
The nucleophilic ring opening of epoxides with amines is a well known route for the synthesis of β-amino alcohols. The use of carbonates offers significant advantages over epoxides as they are far less hazardous mate...The nucleophilic ring opening of epoxides with amines is a well known route for the synthesis of β-amino alcohols. The use of carbonates offers significant advantages over epoxides as they are far less hazardous materials, safe for handling, do not require high-pressure equipment and most notably the possibility of solvent less reactions. In this work, utilization of zeolite as host catalyst in the reaction media for synthesis of β-amino alcohols without using solvent is reported.展开更多
基金the National Natural Science Foundation of China(No.20002002 and No.20272025)Ph.D.programs Foundation of Ministry of Education of China for generous financial support of our program.
文摘A series of optically active N-protected 1,2-amino alcohols were synthesized via the reduction of the corresponding a-aminoketones starting from the readily available L-amino acids.
基金This research was made possible as a result of a generous grant from NSFC(grant nos.21971101 and 22171127)Guangdong Basic and Applied Basic Research Foundation(grant no.2022A1515011806)+3 种基金Department of Education of Guangdong Province(grant nos.2022JGXM054 and 2021KTSCX106)Shenzhen Science and Technology Innovation Committee(grant no.JCYJ20220519201425001)Thousand Talents Program for Young Scholars,The Pearl River Talent Recruitment Program(grant no.2019QN01Y261)Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002).
文摘Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.
文摘A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction conditions.The reaction has a wide substrate scope and operational simplicity.Mechanistic studies suggest that1,2‐carbon migration is induced by regioselective nitrogen‐centered radical addition to the alkene unit.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived β-amino alcohols were synthesized from L-DOPA in good yields. The structures of the target compounds were confirmed by ^1H NMR, ^13C NMR and MS.
文摘Four new chiral 1,2,3,4-tetrahydroisoquinoline-derived G-amino alcohols were synthesized from commercially available LDOPA. These ligands were evaluated in the asymmetric addition of diethylzinc to benzaldehydes and showed different catalytic activities （up to 86% ee）. The solvent played an important role in the enantioselective process. The transition state models were proposed to explain the reversion of the product configuration.
文摘A highly effective,new chiral 1,2,3,4-tetrahydroisoquinoline catalyst 1 for the diethylzinc addition to aryl aldehydes has been investigated.Using 10 mol%of this chiral catalyst,secondary alcohols can be obtained in up to 87%yield and 99.5%ee under mild conditions.
文摘The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the central C=N double bond. It crystallizes in orthorhombic, space group P2dc with a = 7.632（1）, b = 7.816（1）, c = 28.082（5） A,β = 96.18（1）°, V= 1665.48（51） A^3, Z= 4, Dc = 1.341 g/cm^3, F（000） = 704,μ = 0.094 mm^-1, the final R = 0.0448 and wR = 0.1058. Of the total 3748 collections, 3105 were unique. In the molecule there exist two different planes of pyrazoline and C（11）-C（16） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0.03 A） with the dihedral angle between them of 9.8%.
基金This work was supported by the Phytochemistry Key Laboratory of Shaanxi Province (No. 02js40)
文摘The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the C=N double bond. It crystallizes in the monoclinic system, space group P2 1/c with a = 11.150（3）, b = 9.906（3）, c = 13.624（4） A, β = 106.360（4）°, V= 1443.9（7） ,A^3, Z = 4, Dc = 1.294 g/cm^3, F（000） = 592,μ（MoKa） = 0.088 mm ^-1, R = 0.0577 and wR = 0.1214. Of the 5766 total reflections, 2540 were unique. In the molecule there exist two different planes of pyrazoline and O（2）-C（10） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0026 A） with the dihedral angle between them of 6.3°.
文摘The nucleophilic ring opening of epoxides with amines is a well known route for the synthesis of β-amino alcohols. The use of carbonates offers significant advantages over epoxides as they are far less hazardous materials, safe for handling, do not require high-pressure equipment and most notably the possibility of solvent less reactions. In this work, utilization of zeolite as host catalyst in the reaction media for synthesis of β-amino alcohols without using solvent is reported.
