Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The ...Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2=C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α =91.263(14)°,(β = 102.559(6)°,γ= 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four (a-methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist anti-ferromagnetic interactions between the two copper(Ⅱ) atoms.展开更多
An efficient and clean preparation of acylals from aromatic aldehydes in the presence of synthetic phosphates (flourapatite and hydroxyapatite doped with ZnCl2 and ZnBr2) and acetic anhydride was achieved easily in hi...An efficient and clean preparation of acylals from aromatic aldehydes in the presence of synthetic phosphates (flourapatite and hydroxyapatite doped with ZnCl2 and ZnBr2) and acetic anhydride was achieved easily in high yields (86% - 97%) at room temperature under solvent-free conditions. Deprotection of the resulting acylals has also been attained by using the same catalysts under microwave irradiation. This method consistently has advantage of excellent yields (82% - 96%) and a short reaction time (3 - 4 min).展开更多
Recent advances in the desilylative acylation of 1-alkenylsilanes with acid anhydrides under transition metal catalysis are summarized.This catalytic desilylative acylation of 1-alkenylsilanes provides an efficient ro...Recent advances in the desilylative acylation of 1-alkenylsilanes with acid anhydrides under transition metal catalysis are summarized.This catalytic desilylative acylation of 1-alkenylsilanes provides an efficient route toα,β-unsaturated ketones by using rhodium or iridium as the catalyst.Moreover,various one pot sequence reactions have been developed,which can synthesizeα,β-unsaturated ketones from simple starting materials in an economic way.Additionally,this approach is applied to the asymmetric synthesis of atropisomers possessing silanol groups with excellent enantioselectivity.展开更多
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29831010) and the Foundation of the State Key Laboratory of Coordination Chemistry of Nanjing University.
文摘Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2=C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α =91.263(14)°,(β = 102.559(6)°,γ= 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four (a-methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist anti-ferromagnetic interactions between the two copper(Ⅱ) atoms.
文摘An efficient and clean preparation of acylals from aromatic aldehydes in the presence of synthetic phosphates (flourapatite and hydroxyapatite doped with ZnCl2 and ZnBr2) and acetic anhydride was achieved easily in high yields (86% - 97%) at room temperature under solvent-free conditions. Deprotection of the resulting acylals has also been attained by using the same catalysts under microwave irradiation. This method consistently has advantage of excellent yields (82% - 96%) and a short reaction time (3 - 4 min).
基金Financial support from National Natural Science Foundation of China(No.21871053)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01005)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD04)。
文摘Recent advances in the desilylative acylation of 1-alkenylsilanes with acid anhydrides under transition metal catalysis are summarized.This catalytic desilylative acylation of 1-alkenylsilanes provides an efficient route toα,β-unsaturated ketones by using rhodium or iridium as the catalyst.Moreover,various one pot sequence reactions have been developed,which can synthesizeα,β-unsaturated ketones from simple starting materials in an economic way.Additionally,this approach is applied to the asymmetric synthesis of atropisomers possessing silanol groups with excellent enantioselectivity.
