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FeCl_3·6H_2O-catalyzed selective reduction of allylic halides to alkenes with concomitant oxidation of benzylic alcohols to aldehydes

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Science China Chemistry 2014年第2期57卷 282-288页

作者： ZHANG HouCai LIU RuiTing zhou xigeng Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Department of Chemistry Fudan University State Key Laboratory of Organometallic Chemistry

Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective *** method not only features a readily available reductant,an inexpensive catalyst,simple manipulation,and good tolerance of functional groups including nitriles,nitro,esters,and methoxyl groups,it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are ***,this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.

关键词： selective reduction allylic halides Fe-based catalysts hydrodehalogenations benzyi alcohols

Lanthanide-catalyzed cyclocarbonylation and cyclothiocarbonylation: a facile synthesis of benzannulated 1,3-diheteroatom five- and six-membered heterocycles

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Science China Chemistry 2014年第8期57卷 1117-1125页

作者： JING YuFeng LIU RuiTing LIN YangHui zhou xigeng Shanghai Key Laboratory of Molecular Catalysis and Innovative Material Department of Chemistry Fudan University State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry

La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol, o-aminothiophenol, catechols and anilines ortho-substituted by CH2NH2 and CONH2 to form, respectively, the corresponding benzimidazolones, benzoxazolones, benzothiazolones, benzodioxolones, 3,4-dihydroquinazolin-2(1H)-one, and quinazolinediones. These results represent the first example of lanthanide-catalyzed carbonylation. This methodology is also applicable for the preparation of various benzannulated 1,3-diheteroatom cyclic thioketones starting from aryl/alkyl isothiocyanates or CS2 in good to excellent yields. Based on the results of experiments performed using an o-aminobenzamido dianion lanthanide complex, a general mechanism, involving the tandem reaction of two lanthanide-ligand bonds with one heterocumulene molecule, is proposed as well.

关键词： lanthanide catalyst 1 2-disubstituted benzene isocyanate isothiocyanates cyclocarbonylation cyclothiocarbonylation

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A luminescent metal-organic framework with an open cubic cage and eight-coordinate cadmium nodes

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Science China Chemistry 2010年第10期53卷 2079-2082页

作者： WANG ChuanFeng ZHANG ZhengXing ZHANG LiLi LI FuYou zhou xigeng Department of Chemistry Fudan UniversityShanghai 200433China Department of Chemistry Taizhou CollegeLinhai 317000China

Self-assembly of cadmium ions and the rigid bridging ligand 4,4′-methylenebis(3-hydroxy-2-naphthoic acid) (pamoic acid, H4PA) leads to a one-dimensional metal-organic framework with open cube-like M2(H2PA)2 cages wit... 详细信息

关键词： framework eight-coordinate cadmium cubic cage fluorescence pamoic acid

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芳香性稀土金属杂环丙烯化合物

有机化学 2020年第4期40卷 1084-1085页

作者：王凯周锡庚复旦大学化学系上海200433

金属杂环丙烯因其独特的结构、反应性和广泛的应用,在金属有机化学中具有重要的地位.过去四十多年里,d-过渡、主族和锕系金属的杂环丙烯化合物得到了广泛深入研究,展示出了诱人的发展前景[1~4].例如,过渡金属杂环丙烯已成为设计众多过... 详细信息

金属杂环丙烯因其独特的结构、反应性和广泛的应用,在金属有机化学中具有重要的地位.过去四十多年里,d-过渡、主族和锕系金属的杂环丙烯化合物得到了广泛深入研究,展示出了诱人的发展前景[1~4].例如,过渡金属杂环丙烯已成为设计众多过渡金属催化反应,如炔烃羧基化反应等的关键中间体[5];而基于芳香性杂环并过渡金属杂环丙烯中间体的开环反应则为芳环碳-碳键断裂提供了一种新方法[6].此外,炔烃形成金属杂环丙烯反应还是一种保护炔的有效方法[7].继续发展含不同金属的杂环丙烯对深入了解这类化合物的成键性质和内在反应性、拓展其应用至关重要,因为改变金属性质会对金属杂环丙烯配合物的成键性质和反应性产生重要影响,对开发新的炔烃还原偶联反应和设计新的相关炔烃反应催化剂具有指导意义.稀土是元素周期表中最大的一个副族元素,具有独特的电子结构和难以替代的理化性质.

关键词：金属有机化学芳香性元素周期表成键性质反应催化剂锕系金属开环反应金属杂环

Rare-Earth Metal-Catalyzed Addition of Terminal Alkynes to Aryl-Substituted Carbodiimides

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Rare-Earth Metal-Catalyzed Addition of Terminal Alkynes to A...

Synthesis of[(C_5H_5)Y(η~2-PzMe_2)(μ-PzMe_2)]_2 and [Y(η~2-PzMe_2)_2(μ-PzMe_2)(μ-THF)]_2 and the insertion of Me_2SiO into the Y-N bond

第十八届全国金属有机化学学术研讨会

作者： Fangjun Zhang Jie Zhang xigeng zhou Department of Chemistry Fudan University

Nucleophilic addition of terminal alkynes to carbodiimides provides a straightforward method for synthesis of propiolamidines RN=C(C≡CR)*** many organometallic compounds,such as lithium,calcium,magnesium,rare-earth metals compounds have proved to be efficient catalysts for the cross-coupling reaction of terminal alkynes with N,N′-dialkylcarbodiimides, N-aryl-substituted carbodiimides are inefficient substrates in all these catalytic *** this contribution,we would like to report the first example of direct addition of terminal alkynes with N-aryl-substituted carbodiimides catalyzed by rare-earth

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来源： cnki会议评论

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Chinese Science Bulletin 2001年第9期46卷 723-726页

作者： zhou xigeng, ZHANG Libei, RUAN Ruyi, ZHANG Lixin , CAI Ruifang & WENG LinhongDepartment of Chemistry, Fudan University, Shanghai 200433, China State Key Laboratory of Elemental Organic Chemistry, Nankai University, Tianjin 300071, China Department of Chemistry Fudan University Shanghai China State Key Laboratory of Elemental Organic Chemistry Nankai University Tianjin China

3,5-Dimethylpyrazole (HPzMe2) reacted with (C5H5)3Y in THF to yield dinuclear complexes [(C5H5)Y-(η2-PzMe2)(μ-PzMe2)]2 ( I ) and [Y(η2-PzMe2)2(μ-PzMe2)-(μ-THF)]2 (II), revealing a new method for synthesizing tris(pyrazolate) complexes of lanthanide metals. The X-ray crystallographic analysis showed that complex II crystallizes in space group P 1 , with unit cell dimensions a = 1.0798(1), b = 1.0818(1), c = 1.1313(1) nm, a = 76.914(2)°,(B = 68.940(2)°, γ= 60.510(2)°, V = 1.0715(2) nm3, Z = 1. The final R factor is 0.0445. The investigation results showed that Me2SiO can only be inserted into the Y-N (bridging) bond of complex I to form [(C5H5)Y(η2-PzMe2)(μ-OSiMe2 PzMe2)]2 (Ⅲ), but cannot be inserted into the Y-N (bridging) bond of complex II due to the bulky crowding of the tetraple bridge structure.

关键词： yttrium pyrazolate crystal structure synthesis insertion cyclopentadienyl.

STATUS OF SURGICAL TREATMENT OF RECTAL CANCER IN CHINA

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Medical Bulletin of Shanghai Jiaotong University 1990年第1期13卷 30-36页

作者：周锡庚 Section of Colorectal Surgery Department of Surgery Ruijin Hospital SSMU Shanghai

The multimodality treatment methods of rectal cancer in China are presented. Extended radical excisions are used for Dukes’ B and C cases to reduce local recurrence. These include: high ligation with clearance of proximal lymph nodes at origin of inferior mesenteric artery, lateral pelvic lymphadenectomy, posterior or total pelvic exenterations in selected cases; but controversy exists. Radical sphincter-saving resections are advocated to improve the quality of life. Prerequisites of sphincter-saving resection are adequate resection of bowel and mesentery distal to the lesion, depending on the macroscopic type of lesion and degree of differentiation. The decisive factor in the choice of type of operation is the length of rectal stump above levator ani after resection. Bacon’s pull through resection was modified by preservation of levator ani and dentate margin, much better functional results were obtained postoperatively. Transanal full thickness local excision is advocated for small, protuberant, mobile, well differentiated lesions below the peritoneal reflection. Pre- or postoperative adjuvant radiation therapy is sometimes used for Dukes’ B and C cases. Adjuvant 5-Fu chemotherapy is usually used intraoperatively (intraluminal) or postoperatively (intravenous). The superiority of preoperative intrarectal 5-Fu emulsionover the conventional intravenous route has been demonstrated by experimental and clinical studies, which showed much higher and lasting concentration of 5-Fu in the rectal wall tissues and mesenteric lymph nodes, and a much lower concentration of 5-Fu in bone marrow after intrarectal administration. Several surgical groups employed varying techniques of sphincteric reconstruction of perineal colostomy after abdominoperineal excision, utilizing the gracilis or gluteus maximus sling, or intussusception of the colonic stump; with favorable late results in reported cases. However, controversy exists, so strict appropriate case selection is emphasized to

关键词： colorectal cancer lateral pelvic lymphadenectomy pelvic exenteration radical sphincter-saving resections local excision adjuvant therapy preoperative intrarectal 5-Fu perineal colostomy with sphincteric reconstruction

Pd（OAc）2/CuI分步催化合成多取代3-烃硫（硒）基吲哚化合物（英文）

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有机化学 2019年第11期39卷 3215-3222页

作者：刘瑞婷李振王圣克周锡庚复旦大学化学系上海200438 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海20032

发展了一种Pd(OAc)2/CuI分步催化2-(2,2-二溴乙烯基)胺、苯硼酸和联硫(硒)化合物发生偶联/环化/硫烷基化反应合成3-烃硫(硒)基吲哚化合物的新方法.底物中不同的官能团,如甲氧基、氯、三氟甲基在反应中都能很好地兼容.

关键词：吲哚 Pd(OAc)2/CuI 催化合成

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环辛四烯基稀土金属有机配合物

有机化学 2000年第2期20卷 155-167页

作者：张立新周锡庚蔡瑞芳黄祖恩复旦大学化学系上海200433

环辛四烯基稀土配合物是继茂基配合物之后的又一类非常重要的稀土金属有机配合物,本文将就这一领域的发展情况作一个简要的总结和回顾。

关键词：稀土配合物合成结构氧化还原法配体交换法