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Synthesis of Substituted Indenes and N-Fmoc 2-aminoalkanesulfonyl Chlorides

Abstract第7页
摘要第8-9页
Acknowledgements第9-16页
Abbreviations第16-20页
Chapter Ⅰ Synthesis of substituted indenes by AlCl_3-promotedtandem Friedel-Crafts alkylation of cinnamaldehydes and arenes第20-52页
    1.1 Introduction第20-36页
        1.1.1 Synthetic methods of indenes第21-26页
            1.1.1.1 Acid-catalyzed cyclization of phenyl-substituted allylic alcohols第21-22页
            1.1.1.2 Photo cyclization of phenyl-substituted propynes第22-23页
            1.1.1.3 Ring expansion of substituted cyclopropenes第23页
            1.1.1.4 Addition of organometallic reagents to 1-indanones subsequent by dehydration第23-24页
            1.1.1.5 Cyclization of chalcones第24-25页
            1.1.1.6 Transition-metal catalyzed protocols第25-26页
        1.1.2 Tandem Friedel-Crafts reactions第26-36页
            1.1.2.1 Friedel-Crafts reactions第27-28页
            1.1.2.2 Exemples of tandem Friedel-Crafts reactions第28-36页
                1.1.2.2.1 AlCl_3-promoted tandem Friedel-Crafts reactions of arenes and aldehydes第28-29页
                1.1.2.2.2 TFSA or (TFSA-TFA)-promoted tandem Friedel-Crafts reactions of arenes with aromatic aldehydes第29-31页
                1.1.2.2.3 Tandem Friedel-Crafts reactions of sulfides and acyl chlorides第31-33页
                1.1.2.2.4 Tandem Friedel-Crafts acylation/Nazarov cyclization of arenes and α,β-unsaturated acyl chlorides第33-34页
                1.1.2.2.5 A [Cu(OTf)_2]-promoted tandem Friedel Crafts alkylation and cyclization process第34页
                1.1.2.2.6 The TFA-promoted tandem Friedel-Crafts alkylation, cyclization and hydrogen transfer process第34-35页
                1.1.2.2.7 The AlCl_3-catalyzed tandem Friedel-Crafts acylation and alkylation of arenes and 2-alkenoyl chlorides第35-36页
    1.2 Results and Discussion第36-50页
        1.2.1 Proposed synthetic approach to indenes derivatives第36-37页
        1.2.2 Tandem Friedel-Crafts reaction of benzene and cinnamaldehyde第37-39页
        1.2.3 Interpretation of spectra of 3a and 4a第39-42页
        1.2.4 Preparation of indenes derivatives from arenes and cinnamaldehydes第42-45页
        1.2.5 Possible mechanism for AlCl_3-promoted tandem F-C alkylation of arenes with cinnamaldehydes第45-47页
        1.2.6 Tandem Friedel-Crafts reaction of benzene and Cinnamyl alcohol第47-50页
    1.3 Conclusion第50-52页
Chapter Ⅱ Efficient synthesis of N-Fmoc 2-aminoalkanesulfonylchlorides with functionalized side-chains第52-80页
    2.1 Introduction第52-63页
        2.1.1 Sulfonopeptides第52-56页
            2.1.1.1 Synthesis of sulfonopeptides by the N-protected aminoalkanesulfonyl chlorides and amino acid esters or peptide esters第54页
            2.1.1.2 Synthesis of sulfonopeptides by the condensation of N-protected aminoalkanesulfinyl chlorides and subsequent oxidation第54-55页
            2.1.1.3 Synthesis of sulfonopeptides by Mannich—type reaction of N-protected 2. aminoalkanesulfonamides第55-56页
        2.1.2 Solid phase peptide synthesis第56-58页
            2.1.2.1 An example of solid phase peptide synthesis第57-58页
                2.1.2.1.1 Fmoc deprotection第57页
                2.1.2.1.2 Amide bond coupling第57-58页
                2.1.2.1.3 Cleavage第58页
        2.1.3 Protecting groups for solid phase peptide synthesis(SPPS)第58-60页
            2.1.3.1 Fmoc Protecting Group第58-59页
            2.1.3.2 Boc Protecting Group第59-60页
        2.1.4 N-protected 2-aminoalkanesulfonyl chlorides第60-63页
            2.1.4.1 Synthesis of N-protected 2-aminoalkanesulfonyl chlorides from N-protected a-sulf-onic acids第60-61页
            2.1.4.2 Synthesis of N-protected 2-aminoalkanesulfonyl chlorides from their sodium salts,using chlorinating agent第61-63页
                2.1.4.2.1 By using phosgene COCl_2第61-62页
                2.1.4.2.2 By using Triphosgene第62页
                2.1.4.2.3 By using Thionyl chloride第62-63页
            2.1.4.3 Synthesis of sulfonyl chloride by using N-chlorosuccinimide (NCS)第63页
    2.2 Results and Discussion第63-78页
        2.2.1 Synthesis of vatious xanthates 3第64-65页
        2.2.2 Optimization of reaction conditions for synthesis of dithiocarbonates 5第65-66页
        2.2.3 Interpretation of spectra of dithiocarbonate 5h第66-68页
        2.2.4 Synthesis of aminoxanthates 5第68-69页
        2.2.5 Synthesis of various sulfonyl chlorides 2-4第69-71页
        2.2.6 Interpretation of spectra of sulfonyl chloride 6h第71-75页
        2.2.7 Proposed mechanism for the oxidative chlorination thioacetates 5第75-78页
    2.3 Conclusion第78-80页
Chapter Ⅲ Experimental section第80-106页
    3.1 Methods,Skills,and Facilities第80页
    3.2 General procedure for AlCl_3-promoted tandem Friedel-Crafts alkylation of arenes with cinnamaldehydes第80-88页
    3.3 Preparation of(9H-Fluoren-9-yl)methyl allylcarbamate 4第88页
    3.4 General procedure for synthesis of xanthates 3第88-91页
    3.5 General procedure for pynthesis of aminoxanthates 5第91-98页
    3.6 General procedure for the synthesis of sulfonyl chlorides 6 with NCS/HCl as oxidants第98-106页
Chapter Ⅳ Conclusions第106-108页
Publications lists第108-110页
References第110-128页
Appendix第128-174页
Khdra Haiouani, MSc,PhD.(Chemistry)第174-176页
Prof. Dr. Jiaxi Xu第176-177页
研究生学位论文答辩委员会决议书第177-178页

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