摘要
环丙烷衍生物不仅存在于多种天然产物及具有药物活性分子的结构中,而且,由于具有高选择性开环反应性质,该类化合物己被作为一类重要的有机合成中间体,广泛应用于多种天然产物、药物分子以及重要复杂分子的合成。因此,自从慕尼黑有机化学家William Henry Perkin[1]在实验室第一次合成环丙烷衍生物以来,对该类化合物的合成以及开环反应研究一直受到有机合成化学家和药物化学家的高度重视。
在该研究领域中,α-乙酰基环丙烷基酰胺类化合物不仅含有氧和氮等亲核杂原子,同时由于双羰基活化作用,使该类化合物具有很高的反应活性。近年来,对该类化合物在各种碳环、杂环以及稠环化合物合成中的应用研究引起人们广泛关注。然而,相对而言,人们对带有炔基的α-乙酰基环丙烷基酰胺类化合物的开环反应的应用研究以及α-乙酰基环丙烷基酰胺类化合物和异氰基乙酸乙酯的成环反应的研究却十分有限。
本论文以多官能化的α-乙酰基环丙烷基酰胺类化合物为起始原料,重点研究该类化合物与异氰基乙酸乙酯的成环反应以及含有炔基结构单元的α-乙酰基环丙烷基酰胺类化合物的开环和成环反应,合成了一系列重要的氮环和稠杂环类化合物。具体研究内容如下:
1.在Cu2O催化下,成功实现了α-乙酰基环丙烷基酰胺类化合物与异氰基乙酸乙酯分子内成环反应,制备一系列重要的噁唑类化合物。在此基础上,通过控制反应条件,调控反应取向,获得多种重要吡啶酮类化合物。
2.以含有炔基结构单元的α-乙酰基环丙烷基酰胺类化合物为底物,在TsOH·H2O作用下,成功实现该类环丙烷类化合物开环反应以及随后的分子内炔基胺化反应,制备一系列重要的多取代吡咯酮类化合物。
3.在t-BuOK作碱的条件下,成功实现氮原子上含有丙炔基的α-乙酰基环丙烷基酰胺类化合物分子内连续的多米诺成环反应,制备一系列重要的呋喃[3,2-b]-γ-内酰胺类衍生物,为该类化合物在有机化学以及药物化学等领域中的进一步应用奠定了坚实的基础。
4.以丙炔胺类化合物和硫代插烯式硫酯类化合物分别为1,3-偶极子和Cz-亲偶极体,在水相中,成功实现碱驱动或催化二者连续的[3+2]环合反应和随后脱乙酰基或1,2-酰基迁移反应,获得多种重要的多取代吡咯类衍生物。
本文合成了许多的新化合物,并对其进行了1H-NMR、13C-NMR等数据表征。
Cyclopropane derivatives exists in structures of various natural products and moleculeswith medicinal reactivity, due to having a high selectivity for the nature of the ring-openingreaction, the kind of chemical compound is regarded as important organic synthesisintermediate which is widely applied in synthesis of various natural products, medicinalmolecules, and complex molecules. Therefore, since the first cyclopropane derivatives weresynthesized by William Henry Perkin in Munich in the laboratory of the eminent chemistAdolf von Baeyer, the chemists of synthetic and medicinal Chemistry have attached greatattention to the synthesis of the compounds as well as the ring-opening reaction research.
In research of this area,-acetyllcyclopropanylamide not only has nucleophilicheteroatoms like oxygen and nitrogen, but also has double activation of carbonyl, so that thesecompounds have high reactivity. In recent years, the study of the compounds in the synthesisof various carbocyclic and heterocyclic compounds fused on ring has caused widespreadconcern. However, researches in ring-opening reaction of-acetyllcyclopropanylamide withalkynyl and cyclization reaction of ethyl isocyanoacetate is very limited.
In this thesis, taking polyfunctional-acetyllcyclopropanylamide as original material,focuses on cyclization reaction of this compound and ethyl isocyanoacetate, as well asring-opening and cyclization reaction of-acetyllcyclopropanylamide with alkynyl unit, andsynthetised a series of important nitrogen ring and heterocycle compound. The followingstatements are the brief of my work.First, a series of oxazole compounds were obtained via AuCl3-catalyzed the successiveintermolecular condensation and intramolecular cyclization reaction of
-acetyllcyclopropanylamide and ethyl isocyanoacetate. Basing on this, various importantpyridine compounds are obtained through controlling reaction conditions.Second, a series of polysubstituted pyrollidone compounds were obtained via the action ofTsOH H2O, taking-acetyllcyclopropanylamide with alkynyl unit as substrate, ring-openingreaction and the subsequent intramolecular alkynylamine reaction.Third, a series of furan[3,2-b]--lactam compounds were obtained via the action of t-BuOK,domino reactions of-acetyllcyclopropanylamide with alkynyl on nitrogen-atomsnitrogen-atoms. All this laid a solid foundation on further application in organic chemistry andmedicinal chemistry.
Fourth, various important polysubstituted pyrrole derivatives are obtained via [3+2] Cycloadditionsof-acyl ketene dithioacetals with propargylamines and1,2-acyl migration reaction, whichare under base actiom, taking propargylamines compounds and thioester interpolation olefinic compounds as1,3–dipole and C2-dipolarophile.
In this thesis, many new compounds were synthesized and characterized by confirmed by1HNMR and13CNMR spectroscopies.
引文
[1]Perkin, W. H. Ber. Dtsch. Chem. Ges.[M] New York: Addison Wesley,1884,17,54.
[2]Wallach, O. Terpene und Campher; Veit&Comp.: Leipzig, Terpenes and Camphor Germany,1909.
[3]Staudinger, H.; Ruzicka, L. HelV. Chim. Acta1924,7,177.
[4]Staudinger, H.; Ruzicka, L. HelV. Chim. Acta1924,7,201.
[5]Beckmann, S.; Geiger, H. In Methoden der Organischen Chemie (Houben-Weyl); Mu¨ller, E., Ed.;Thieme: Stuttgart, Germany,1971;4,445.
[6]Wessjohann, L.; A.; Brandt, W.; Thiemann, T.; Biosynthesis and Metabolism of Cyclopropane Rings inNatural Compounds [J].Chem. Soc. Rev.2003,103,1625.
[7]Yoshida, M.; Ezaki, M.; Hashimoto, M.; Yamashita, M.; Shigematsu,N.; Okuhara, M.; Horikoshi, K. J.Antibiot.1990,18,748.
[8]Leeper, F. J.; Shaw, S. E.; Satish, P.; Can. J. The biosynthesis of porphyrins, chlorophylls, and vitamin.[J]. Chem. Soc. Rev.1994,72,131
[9] Mulheirn, L. J.; Ramm, P. J. The biosynthesis sterols. Chem. Soc. Rev.1972,1,259.
[10]Sobti, R.; Dev, S.;(+)-Trans-Chrysanthemic acid from (+)-3-Caren. Tetrahedron.1974,30,2927.
[11]Burger, W.; L.; L. Yost. Arylcyclo alkylamines. I.2-Phenylcyclopropylamine. J. Am. Chem. Soc.1948,70,2198.
[12]Simmons, H.; E.; Smith, R.; D.; A new synthesis of cynthesis of cyclopropanes from plefins[J]. J. Am.Chem. Soc,1958,80,5323.
[13]Kawabata, N.; Aameura, I.; Naka, M.; Synthesis of cyclopropane derivatives from olefins by thereaction with organic gem-dihalides and copper [J]. J. Am. Chem. Soc,1979,101:2139.
[14]Bartleson, J.; D.; Burk, R.; E.; Lankelma, H.; P.; The Preparation and Identification ofAlkylcyclopropanes:1,1,2-Trimethyl-cyclopropane and1,2-Dimethyl-3-ethylcyclopropane [J]. J. Am.Chem. Soc,1946,68,2513.
[15]Shortsidge R N. et al., ibid.1948,70:946.
[16]Brooks, B.; T.,;The Chemistry of the Nonbenzenoid Hydrocarbons (New York)1950,88.268.
[17]Simmons, H.; E.; Smith, R.; D.; A new synthesis of cynthesis of cyclopropanes from plefins.[J]. J. Am.Chem. Soc,1958,80,5323.
[18]Ronald, B.; Judd, P.; Adolf, K.; Synthesis of Cyclopropenones by a Modified Favorskii Reaction. J. Am.Chem. Soc.1963,85,234.
[19]Ryan, P.; Wurz, André B.;Charette.; An Expedient and Practical Method for the Synthesis of a DiverseSeries of Cyclopropane-Amino Acids and Amines. J. Org. Chem.2004,69,1262.
[20]Parry, R. J.; Mhaskar, S. V.; Lin, M.-T.; Walker, A. E.; Mafoti, R. Can. J. Am. Chem. Soc,1994,72,86.
[21]1) Munoz, M.; Mendez, C.; Nevado, D.; J.; Cardenas, A.; M.; Synthesis2003,2898;2) Matute, C.; B.;M.; Nevado, D.; J.; Cardenas, A.; M.; J. Am. Chem. Soc.2003,125,5757;3) Mendez, M.; P.; Munoz,A.; M.; Echavarren, J. Am. Chem. Soc.2000,122,11549.
[22]Michael, R.; Luzung, J.; P.; Markham, and Toste, F.; D.; Catalaytic Isomerization of1,5-Enynes toBicyclo[3.1.0]hexenes. J. Am. Chem. Soc.2004,126,10858.
[23]Jochanan, B.; Hanita, B.; K.;, and Yacoub, B.; A Novel PtCL-Catalyzed Cyclorearrangement of AllylPropynyl Ethers to3-Oxabicyclo[4.1.0] heptenest. J. Org. Chem.1995,60,5567.
[24]Mao, Z.; J.; Qu, H.; Q.; Zhao, Y.; Y.; Lin, X.; F.; A general access to1,1-cyclopropane aminoketonesand their conversion into2-benzoyl quinolines, Chem. Commun.,2012,48,9927.
[25]Yadav, A.; K.; Peruncheralathan, S.; H,.;Junjappa H. Domino Carbocationic Rearrangementofr-[Bis(methylthio)methylene]alkyl-2-(3/2-indolyl) Cyclopropyl Ketones [J]. J. Org. Chem,2007,72:1388.
[26]John, E.; M.; Jack, E.; B.; Rodolfo, M.; Robert, M.; A.; Timothy, D.; W.; C.; and Barbara, O.;Biomimetic Synthesis of the Crispatene Core. Org. Lett.,2003,5,5,661.
[27]Wendy, E.; Marcin, J.; Piotr, K.; Katarzyna, Z.; Baldur, S.; and Aleksandra, J.; Reactivity of13,13-Dibromo-2,4,9,11-tetraoxadispiro[5.0.5.1]tridecane toward Organolithiums: RemarkableResistance to the DMS Rearrangement.J. Org. Chem.2008,73,5732.
[28]Tochtermann,W.; Panitzsch, T.; Peschanel, M.; Wolff, C.; Peters, E. M.; Peters,K.; von Schnering, H. G.Liebigs Ann./Recl.1997,11,25.
[29]Hart, H.; Law, P. A. Reactions of tricyclopropylcarbionl derivatives. J. Am. Chem. Soc.1962,84,2462.
[30]Carey, F.; A.; Tremper, H.; S.; Carbonium Ion-Silane Hydride Transfer Reactions. III.Cyclopropylmethyl Cations J. Am. Chem. Soc.1969,91,2967.
[31]Balsamo, C.; Battistini, P.; Crotti, B.; Macchia, F.; The Nucleophilic Step of the Ring OpeningReactions of Cyclopropanes with Electrophiles. Mechanism and Stereochemistry. I. Reaction of1-Phenylbicyclo [4.1.0] heptane with Mercuric Salts. J. Org. Chem.1975,40,22,3233.
[32]David, B.; C.; Fariborz, M.; and John, S.; H.; J. Am. Chem. Soc.,1983,105,23,6882.
[33]Qu, J.; P.; Liang, Y.; Xu, H.; Tang, Y.; Highly Diastereoselective Construction of Fused Carbocyclesfrom Cyclopropane-1,1-dicarboxylates and Cyclic Enol Silyl Ethers: Scope, Mechanism, and Origin ofDiastereoselectivity. Chemistry. A. European. Journal.2000.18(8),2196.
[34]Andrew, T.; Parsons, Austin.; G. S.; Andrew, J. Jeffrey, S.; Johnson Dynamic Kinetic AsymmetricSynthesis of Substituted Pyrrolidines from Racemic Cyclopropanes and Aldimines: ReactionDevelopment and Mechanistic Insights. J. Am. Chem. Soc.2010,132(28),9688.
[35]Zhou, Y.; Y.; Wang, L.; J.; Li, J.; Sun, X.; L.; Yong, T.;.Side-Arm-Promoted Highly EnantioselectiveRing-Opening Reactions and Kinetic Resolution of Donor Acceptor Cyclopropanes with Amines. J.Am. Chem. Soc.2012,134,9066.
[36]Jurgen, B.; Robert, M.; Novel Platinum-Catalyzed Ring-Opening of1,2-Cyclopropanated Sugars withAlcohols.Stereoselective Synthesis of2-C-Branched Glycosides. J. Am. Chem. Soc.1998,120,12137.
[37]Ming, Y.; Vincent, L.; and Brian, L.; Pagenkopf Intramolecular Cyclopropanation ofGlycals: Studiestoward the Synthesisof Canadensolide, Sporothriolide, and Xylobovide Org. Lett.,2001,3,16,2563.
[38]Zhang, J.; Schmalz, H.; G.; Gold(I)-Catalyzed Reaction of1-(1-Alkynyl)-cyclopropyl Ketones withNucleophiles; A Modular Entry to Highly Substituted Furans, Angew. Chem. Int. Ed.2006,45,6704.
[39]Zhang, Z.; Zhang, Q.; Sun, S.; Domino Ring-Opening/Recyclization Reactions of Doubly ActivatedCyclopropanes as a Strategy for the Synthesis of Furoquinoline Derivatives. Angew. Chem. Int. Ed,2007,46:1726.
[40]Xiong, T.; Zhang, Q.; Zhang Z.; A Divergent Synthesis of-Iminolactones, Dihydroquinolin-2-ones,and-Lactames from-Hydroxymethyl cyclopropanylamides. J. Org Chem,2007,72,(21),8005.
[41]Zhang, Z.; G.; Xue, C.; Liu, X.; Zhang, Q.; Liu, Q.; Synthesis of polysubstituted3H-pyrimidin-4-onesfrom cyanoacetamides under Vilsmeier conditions, Tetrahedron,2011,67,7081.
[42]Tina N, Grant and F. G. West Interrupted Nazarov Reactions Using Dichlorocyclopropanes: A NovelMode of Arene Trapping [J]. Org. Lett,2007,9,3789.
[43]Yadav V K, Balamurugan R. Silicon-Assisted Ring Opening of Donor-Acceptor SubstitutedCyclopropanes. An Expedient Entry to Substituted Dihydrofurans [J]. Org. Lett,2001,3,2717.
[44]Liu L, Montgomery J. Dimerization of Cyclopropyl Ketones and Crossed Reactions of CyclopropylKetones with Enones as an Entry to Five-Membered Rings [J]. J. Am. Chem. Soc,2006,128,5348.
[45]Pellacani, L.; Tardella, A.;P. Cyclopropane Ring Opening with Pyridine Hydrochloride. J. Org. Chem.1975,41,7,1976.
[46]Pohlhaus, P.; D.; Johnson, J.; S.; Highly Diastereoselective Synthesis of etrahydrofurans via LewisAcid-Catalyzed Cyclopropane/Aldehyde Cycloadditions. J. Org. Chem.2005,70,1057.
[47]1)Pan, W.; Dong, D.; W.; Efficient One-Pot Synthesis of Highly Substituted Pyridin-2(1H)-ones viathe Vilsmeier-Haack Reaction of1-Acetyl,1-Carbamoyl Cyclopropanes [J]. Org. Lett,2007,9,(12),2421..2) Xiang, D.; Wang, K.; Liang, Y.; A Facile and Efficient Synthesis of PolyfunctionalizedPyridin-2(1H)-ones from-Oxo Amides under Vilsmeier Conditions. Org. Lett,2008,10,(2),345.
[48]1)Wang, K.; Xiang, D.; Liu, J.; Efficient and Divergent Synthesis of Fully Substituted1H-Pyrazolesand Isoxazoles from Cyclopropyl Oximes. Org Lett,2008,10(9):1691.2)Wang, K.; Fu, X.; Liu, J.;PIFA-Mediated Oxidative Cyclization of1-Carbamoyl-1-oximylcycloalkanes: Synthesis ofSpiro-Fused Pyrazolin-5-one N-Oxides. Org Lett,2009,11,(4),1015.
[49]Liang, F.; S.; Lin, S.; X.; Wei, Y.; Aza-oxy-carbanion relay via non-brook rearrang ement: dfficientsynthesis of furo[3,2-c]pyridinones, J. Am. Chem. Soc.2011,133,1781.
[50]Wang, Y.; Lin, S.; X.; Zhang, J.; Niu, Z.; H.; Fu, Q.; Liang, F.; S,; Halonium-initiated electrophiliccascades of1-alkenoycloprpane carboxamides: efficient access to dihydrofur pyridinones and3(2H)-furanones, Chem.Commun.2011,47,12394.
[51]Liang, F.; S; S; Lin, S.; X.; Wei, Y.; Aza-oxy-carbanion relay via non-brook rearrang ement: dfficientsynthesis of furo[3,2-c]pyridinones, J. Am. Chem. Soc.2011,133,1781.
[52]Liang, F.; S,; Cheng, X.; Lin, J.; Lin, Q.; Efficient three-component one-oot synthesis of fullysubstituted pyridin-2(1H)-ones via tandem Knoevenagel condensation-ring-opening ofcyclopropane-intramolecular cyclization, Chem. Commun.,2009,24,3636.
[53]Kseniya, N.; Sedenkova, E.; B.; Averina, Y.; K.; Grishin, A.; G.; Kutateladze, Victor, B.; Rybakov, T.;S.; Three-Component Heterocyclization of gem-Bromofluorocyclopropanes with NOBF4: Access to4-Fluoropyrimidine N-Oxides, J. Org. Chem.2012,77,9893.
[54]Yadav, A.; K.; Peruncheralathan, S.; Ila, H.; Junjappa, H.; Domino Carbocationic Rearran gement ofr-[Bis(methylthio) methylene] alkyl-2-(3/2-indolyl) Cyclopropyl Ketones. J. Org. Chem,2007,72,1388.
[55]Shi M, Tang X, and Yang Y. Lewis Acid Mediated Reactions of1-Cyclopropyl-2-aryleth anones withAllenic Esters: A Facile Synthetic Protocol for the Preparation of Dihydrofuro[2,3-h]chromen-2-oneDerivatives [J]. Org. Lett,2007,9,4017.
[56]Yang, Y.; and Shi, M.; Ring-Expanding Reaction of Cyclopropyl Amides with Triphenyl phosphine andCarbon Tetrahalide [J]. J. Org. Chem,2005,70,8645.
[57]Zhang, L.; J.; Xu, X.; X.; Xia, W.; M.; Liu, Q.; Bicyclization of isocyanides; a synthetic strategy forfused pyrroles, Adv,. Synth. Catal.,2011,353,2619.
[58]Mao, Z.; Qu, H.; Q.; Zhao, Y.; A general access to1,1-cyclopropane aminoketones and their conversioninto2-benzoyl quinolines, Chem. Commun.,2012,48,9927.
[59]Celerier, J. P.; Haddad, M.; Jacoby.; D. Heterocyclization of Primary Amines With Highly ActivatedCyclopropanes: A New Route to Isoretronecanol. Tetrahedron. Lett,1987,28,(52),6597.
[60]Masahiro T, Minoru U, Takafum M. One-Step Synthesis Heteroaromatic-Fused Pyrrolidines viaCyclopropane Ring-Opening Reaction: Application to the PKCa Inhibitor JTT-010.[J]. Org. Lett,2007,9,3331.
[61]Fuyuhiko, I.; Katsuya, S.; Yusuke, M.; Chisato, M.;.Rhodium(I)-Catalyzed Intramolecular [5+2]Cycloaddition Reactionsof Alkynes and Allenyl cyclopropanes: Construction of Bicyclo-
[5.4.0]undecatrienes and Bicyclo[5.5.0] dodecatrienes*.Angew. Chem. Int. Ed.2010,49,2206.
[62]Minoru, H.; S.; Tadashi, O.; Meng, Y.; M.; Kazuhiko, Rhodium(I)-Catalyzed RegioselectiveRing-Expanding Rearrangement of Allenylcyclo-propanes into Methylenecyclopentenes**. Angew.Chem. Int. Ed.1998,37,1433.
[63]Olga, A. Ivanova, E.; M.; Budynina, Yu.; K.; Grishin, I.; V.; T.; and Pavel, V.; V.; Donor–AcceptorCyclopropanes as Three-Carbon Components in a [4+3] Cycloaddition Reaction with1,3-Diphenylisobenzofuran. Angew. Chem. Int. Ed.2008,47,1107.
[64]Xu, X.; F.; Liu, P.; Adam, L.; Lauren, E. S, Paul, A.; W.; Ligand E ects on Rates andRegioselectivities of Rh(I)-Catalyzed (5+2) Cycloadditions: A Computational Study ofCyclooctadiene and Dinaphthocyclooctatetraene as Ligands. J. Am. Chem. Soc.2012,134,11012.
[65]Angela, M.; Bernard, A.; F.; Francesco, S.; and Pier, P.; P.;2,2-Dimethyl cyclopentanones by acidcatalyzed ring expansion of isopropenylcyclobutanols. A short synthesis of (±)--cuparenone and(±)-herbertene [J]. Chem. Commun,2005,3853.
[66]Shu, D.; X.; Li, X.; X.; Zhang, M.; Patrick, J.; Synthesis of Highly Functionalized Cyclohe xenoneRings: Rhodium-Catalyzed1,3-Acyloxy Migration and Subsequent [5+1] Cycloaddition.Angew. Chem.Int. Ed.2011,50,1346.
[67]Smith, A.; G.; Slade, M.; C.; and Johnson, J.; S.; Cyclopropane-Aldehyde Annulations at QuaternaryDonor Sites: Stereoselective Access to Highly Substituted Tetrahydrofurans. Org. Lett,2011,13(8),1996.
[1]Johan, H.; Nicholas M, Bonham, U.; N.; Cyclic HIV-1Protease Inhibitors Derived from Mannitol:Synthesis, Inhibitory. Potencies, and Computational Predictions of Binding Affinities. J. Med. Chem.1997,40,885.
[2]Pan, Y.; M.; Zheng, F.; J.; Lin, H.; X.; and Zhan, Z.; P.; Br nsted Acid-CatalyzedPropargylation/Cycloisomerization Tandem Reaction: One-Pot Synthesis of Substituted Oxazoles fromPropargylic Alcohols and Amides. J. Org. Chem.2009,74,3148.
[3]Kumar, m.; p.; and Liu, R.; S.; Zn(OTf)2-Catalyzed Cyclization of Proparyl Alcohols with Anilines,Phenols, and Amides for Synthesis of Indoles, Benzofurans, and Oxazoles through Different AnnulationMechanisms. J. Org. Chem.2006,71,4951.
[4]Li, Y.; F.; Xu, X.; X.; Tan, J.; Xia, C.; Y.; Zhang, D.; W.; and Liu, Q.; Double Isocyanide Cyclization: ASynthetic Strategy for Two-Carbon-Tethered Pyrrole/Oxazole Pairs. J. Am. Chem. Soc.2011,133,1775.
[5]Zhang,J.; M.; Coqueron, P.; Y.; Vors, J.; P.; and Ciufolini, M.; A.; Synthesis of5-Amino-oxazole-4-carboxylates from-Chloroglycinates. Org. Lett.,2010,12,(17),3942.
[6]Wipf, P.; Aoyama, Y.; and Benedum, T.; E.; A Practical Method for Oxazole Synthesis byCycloisomerization of Propargyl Amides. Org. Lett.2004,6(20),3593.
[7]Creary, X.; and Losch, A.; Hydroxy--Thiolactams to Oxazole-2-thiones. A Novel DMSO-PromotedOxidation. Org. Lett.2008,10(21),4975.
[8]Hantzsch, A. Condensationprodukte aus Aldehydammoniak and Ketoniartigen Verbindungen.Chemische Berichte.1881,14,1637.
[9]Hidetomo. I, Keiichi. N Masao. H, and Ken. T, Convergent and Rapid Assembly of Substituted2-Pyridones through Formation of N-Alkenyl Alkynylamides Followed by Gold-CatalyzedCycloisomerization. Org. Lett.2008.10.3563.
[10]Masaya. F. j, Takuya. N, Takahiro. K, Satoshi. Y, and Tohru F,2Pyridone Synthesis Using2(Phenylsulfinyl)acetamide. Org. Lett.2012.15,234.
[11]Yuan, Y,; Li, X.; Ding, K.; L.; Acid-Free Aza Diels Alder Reaction of Danishefsky’s Diene withImines. Org. Lett.2002.4.3309.
[12]Huang, P.; Zhang, N.; Zhang, R.; andDong, D.; W.; Vilsmeier-Type Reaction of Dimethylaminoalkenoyl Cyclopropanes: One-Pot Access to2,3-Dihydrofuro [3,2-c]pyridin-4(5H)-ones. Org.Lett.2012.14.370.
[13]Chun, Y.; S.; Lee, J.; H.; Kim, J.; H.; Ko, Y.; and Lee, S., G.; Tandem One-Pot Synthesis ofPolysubstituted Pyridines Using the Blaise Reaction Intermediate and1,3-Enynes. Org. Lett.2011.13.6390.
[14]Zhang, Z.; G.; Fang, S,; L.; Liu, Q.; F.; and Zhang, G.; S.; Approach to Polysubstituted4Pyridones fromAryl Acetoacetamides via a N to C1,3-Acyl Migration Mediated by Sodium Persulfate. J. Org. Chem.2012,77,7665.
[15]Llorente V. R.; Zhang, H.; C.; Diane, A.; G.; Indrasena, R.; and Bruce, E.; M.; Cobalt-MediatedMacrocyclizations. Facile Synthesis of2-OxoPyridino phanes via [2+2+2] Cycloaddition of,-Diynesand Isocyanates. Org. Lett.2003. Vol.5.4537.
[16]1) Bi, X.; H.; Dong, D.; W.; Liu, Q.;[5+1] Annulation: A Synthetic Strategy for Highly SubstitutedPhenols and Cyclohexenones. J. Am. Chem. Soc,2005,127(13):4578.2) Dong, D.; W.; Bi, X.; H.; Liu,Q.;[5C+1N]Annulation: a novel synthetic strategy for functionalized2,3-dihydro-4-pyridones. Chem.Commun,2005,(28):3580.3) Bi, X.; H.; Dong, D.; W.; Li, Y.;[5C+1S] Annulation: A Facile andEfficient Synthetic Route toward Functionalized2,3-Dihydrothiopyran-4-ones. J. Org. Chem,2005,70(26):10886.
[17]Zhao, L.; Liang, F.; S.; Bi, X.; H.; Efficient Synthesis of Highly Functionalized Dihydropyrido[2,3-d]pyrimidines by a Double Annulation Strategy from r-Alkenoyl-r-carbamoyl Ketene-(S,S)-acetals.J. Org. Chem,2006,71(3):1094.
[18]Liu J., Liang, F.; S.; Liu, Q.; BF3·Et2O-Mediated C-C Bond-forming Reaction of-Hydroxyketene-(S,S)-acetals with Active Methylene Compounds and its Application in the Synthesis ofSubstituted3,4-Dihydro-2-pyridones. Synlett,2007,(1):156.
[19]Orazio A A.; Lucia De, C.; Gianfranco, F.; Fabio, M.; and Simona, N.; Divergent RegioselectiveSynthesis of2,5,6,7-Tetrahydro-1H-1,4-diazepin-2-ones and5H-1,4-Benzod iazepines. J. Org. Chem,2011,76,8320.
[20]Xiang, D.; Yang, Y,; R.; Zhang, et al. Vilsmeier-Haack Reactions of2-Arylamino-3-acetyl-5,6-dihydro-4H-pyrans toward the Synthesis of Highly Substituted Pyridin-2(1H)-ones [J]. J OrgChem,2007,72(22):8593.
[21]Takaya, H.; Kojima, S.; and Murahashi, S.; I.; Rhodium Complex-Catalyzed Reaction of Isonitrileswith Carbonyl Compounds: Catalytic Synthesis of Pyrroles. Org. Lett.,2001,3(3),421.
[22]Kim, H.; Y.; and Oh, K.; Highly Diastereo-and Enantioselective Aldol Reaction of Methylr-Isocyanoacetate: A Cooperative Catalysis Approach. Org. Lett.,2011,13(63),1306.
[1]Christian, H.; Peter, L.; Synthesis of5-alkylidene-2,5-dihydropyrrol-2-ones based on cyclizations of1,3-bis(trimethylsilyloxy)-1,3-butadienes with oxalyl chloride. Tetrahedron,2009,65,4530.
[2]Mariella, P.; Fabrizio, R.; Accorsia, L.; Parsons, A.; Ghelf, F.; Functional rearrangement of3-Cl or3,3-diCl-g-lactams bearing a secondary1-chloroalkyl substituent at C-4. Tetrahedron,2010,66,1357.
[3]Gupton, J.; Nakul, T.; Bannera,E.; Kluballa, E.; J.;Halla, K.; E.; et al. The application of (Z)-3-aryl-3-haloenoic acids to the synthesis of.(Z)-5-benzy lidene-4-arylpyrrol-2(5H)-ones. Tetrahedron,2010,66,9113.
[4]Loke, I, Park, N.; Kempf, K.; Jagusch, C.; Schobert, R.; Sabine Lascha, S.; Influence of stericparameters on the synthesis of tetramates from a-amino-b-alkoxy-esters and Ph3PCCO. Tetrahedron,68,2012,697.
[5]Adib, M.; Mahdavi, M.; Noghani, M.; A.; and Bijanzadeh, H.; R.; Reaction between isocyanides andchalcones: an ecient solvent-free synthesis of5-hydroxy-3,5-diaryl-1,5-dihydro-2H-pyrrol-2-ones.Tetrahedron, Letters,2007,48,8056.
[6]Yang, Q.; Lai, Y.; Y.; Xiao, W.; J.; Alperb, H.; Effcient synthesis of4-vinyl a,b-unsaturated c-lactams byring-closing enyne metathesis reactions. Tetrahedron, Letters,2008,49,7334.
[7]Barluenga, J.; Fa anás, F.; J.; Foubelo, F.; Yus, M.; One-pot synthesis of,-unsaturated butyralactamsfrom allyl amines. Tetrahedron Letters,1988.29(38),4859.
[8]Francesco, L.; Giovanni, M.; Angela, S.; Orazio, N.; Saverio, C.; Marco, C.; Leonardo, P.; Giovanni, P.;Angelo, C.; Toward a fragment-based approach to MMPs inhibitors: an expedite and effcient synthesisof N-hydroxylactams. Tetrahedron. Letters,2012,53,4114.
[9]Claudio, C.; Beatrice, R.; Lucia, B.; Gloria, R.; Vincenzo, Z.; Giorgio, P.; Giovanni, C.; and Franca, Z.;Catalytic, Asymmetric Vinylogous Mukaiyama Aldol Reactions of Pyrrole-and Furan-Based DienoxySilanes: How the Diene Heteroatom Impacts Stereocontrol. Adv. Synth. Catal.2010,352,2011.
[10]Nedolya, N.; A.; Schlyakhtina, N.; I.; Valentina, P.; Z.; et, al. Synthesis and Ag+-catalyzed cyclizationof2,3-dienamides. Tetrahedron Letters,2002,43,1569.
[11]Ma, S.; G.; and Ni, B.; K.; Unexpected Dramatic Substituent Effect for Tuning the Selectivity in theDouble Ring-Closing Metathesis Reaction of N-Containing Tetraenes. An Efficient Synthesis ofBicyclic Izidine Alkaloid Skeletons. Org. Lett.,2002,4,639.
[12]Benneche,T.; Chamgordani, E.; J.; Reimer, I.; A new synthesis of fve-membered heterocyclic quorumsensing inhibitors. Tetrahedron. Letters.2012,53,6982.
[1]Claudio, P.; Francesca, V.; and Antonino, F.; Chiral Building Blocks from1,4:3,6-Dianhy drohexitols.III. An Expeditious Enantiospecific Synthesis of the Geissman-Waiss Lactone. Tetrahedron. Lett,1995,36(44):8127.
[2]Francisco, C.; G.; Herrera, A.; J.; Martíná, et al. Intramolecular1,5-hydrogen atom transfer reactionpromoted by phosphoramidyl and carbamoylradicals: synthesis of2-amino-C-glycosides [J].Tetrahedron Lett,2007,48(36):6384.
[3]Jury, J.; C.; Swamy, N.; K.; Yazici, A.; Metal-Catalyzed Cycloisomerization Reactions ofcis-4-Hydroxy-5-alkynylpyrrolidinones and cis-5-Hydroxy-6-alkynylpiperidinones: Synthesis of Furo[3,2-b] pyrroles and Furo[3,2-b]pyridines [J]. J. Org.Chem,2009,74(15):5523.
[4]Ryu, Y.; Kim, G.; A Practical and Divergent Way toTrihydroxylated Pyrrolidine Derivatives as PotentialGlycosidase Inhibitors via StereoselectiveIntermolecular cis-Amidoalkylations [J]. J. Org. Chem,1995,60(1):103.
[5]Lin, G.; Shi, Z.; Enantiomerically pure cage-shaped (1S,4S,5R)-4-hydroxy-2,6-diazabicyclo
[3.3.0]octane and (1S,4R,5R)-4-hydroxy-2-oxa-6-azabicyclo[3.3.0]octane: Synthesis and test forenantioselective catalysis [J]. Tetrahedron,1997,53(4):1369.
[6]Coleman, R.; S.; Walczak, M.; C.; Campbell E L, Total Synthesis of Lucilactaene, A Cell Cycle InhibitorActive inp53-Inactive Cells [J]. J. Am. Chem. Soc,2005,127(46):16038.
[7]Yamaguchi, J.; Kakeya H, UnoT, et al. Determination by Asymmetric Total Synthesis of the AbsoluteConfiguration of Lucilactaene, a Cell-Cycle Inhibitor in p53-Transfected Cancer Cells [J]. Angew. Chem.Int. Ed,2005,44(20):3110.
[8]Sparey, T.; Abeywickrema, P.; Almond, S.; Brandon, N.; Byrne, N.; et al. The discovery of fused pyrrolecarboxylic acids as novel, potent D D-amino acid oxidase (DAO) inhibitors. Bioorganic&MedicinalChemistry Letters2008,18,3386.
[1]Hantzsch, A.; Neue Bildungsweise von Pyrrolderivaten[J]. Ber Dtsch Chem Ges[J].1890,23:1474.
[2]a) Knorr, L.; Synthese von Pyrrolderivaten[J]. Ber Dtsch Chem Ges,1884,17(2):1635-1642; b) Paal, C.;Synthese von Thiophen-und Pyrrolderivaten[J]. Ber Dtsch Chem Ges,1885,18(1):367.
[3]a) Barton, D.; H.; R.; Zard, S.; J.; A new synthesis of pyrroles from nitroalkenes[J]. J Chem Soc, ChemCommun,1985(16):1098-1100; b) Barton, D.; H.; R.; Kervagoret, J.; Zard, S.; J.; A UsefulSynthesis ofPyrroles from Nitroolefins[J]. Tetrahedron,1990,46(21):7587.
[4]Wang, Y.; M.; Bi, X.; H.; Li, D,; H.; Liao, P.; Q.; Wang, Y.; D.; Yang, J.; Zhang, Q.; and Liu, Q.; Iron-catalyzed Synthesis of Polysubstituted Pyrroles via[4C+1N] Cyclization of4-Acetylenic Ketones withPrimary Amines. Chem Commun,2011,47(2):809.
[5]Kramer, S.; Madsen, J.; L.; Skrydstrup, T.; Access to2,5-Diamidopyrroles and2,5-Diamido furans byAu(I)-Catalyzed Double Hydroamination or Hydration of1,3-Diynes. Org Lett,2010,12(12):2758.
[6]Arcadi, A.; Giuseppe, S.; D.; Marinelli, F.; et al. Gold-Catalyzed Sequential Amination/AnnulationReactions of2-Propynyl-1,3-dicarbonyl Compounds[J]. Adv Synth Catal,2001,343(5):443.
[7]Gorin, D.; J, Davis, N.; R, Toste, F.; D. Gold(I)-Catalyzed Intramolecular Acetylenic SchmidtReaction[J]. J Am Chem Soc,2005,127(32):11260.
[8] Saito, A.; Konishi, T.; Hanzawa, Y. Synthesis of Pyrroles by Gold(I)-Catalyzed Amino-ClaisenRearrangement of N-Propargyl Enaminone Derivatives[J]. Org Lett,2010,12(2):372-374.
[9]Kim, J.; T.; Kel, A.; V.; and Gevorgyan, V.;1,2-Migration of the Thio Group in Allenyl Sulfides:Efficient Synthesis of3-Thio-Substituted Furans and Pyrroles**. Angew. Chem. Int. Ed.2003,42,98.
[10]Ackermann, L.; Sandmann, R.; and Kaspar, L.; T.; Two Titanium-Catalyzed Reaction Sequences forSyntheses of Pyrroles from (E/Z)-Chloroenynes or–Haloalkynols. Org. Lett.,2009,9,11,2031.
[11]Merkul, E.; Boersch, C.; Frank, W.; et al. Three-Component Synthesis of N-Boc-4-iodo pyrroles andSequential One-Pot Alkynylation|.2010,11(11):2269..
[12]Wang, Y.; F.; Toh, K.; K.; Chiba, S.; and Narasaka, K.; Mn(III)-Catalyzed Synthesis of Pyrroles fromVinyl Azides and1,3-Dicarbonyl Compounds. Org. Lett.2008,10(21):5019.
[13]Larionov, O.; V.; and Meijere, A.; Versatile Direct Synthesis of Oligosubstituted Pyrroles byCycloaddition of a-Metalated Isocyanides to Acetylenes**. Angew. Chem. Int. Ed.2005,44,5664.
[14]Harrison, T.; J, Kozak, J.; A, et al. Pyrrole Synthesis Catalyzed by AgOTf or Cationic Au(I)Complexes[J]. J Org Chem,2006,71(12):4525.
[15] Liu, W, Jiang, H.; Huangn L.; One-Pot Silver-Catalyzed and PIDA-Mediated Sequential Reactions:Synthesis of Polysubstituted Pyrroles Directly from Alkynoates and Amines[J]. Org Lett,2010,12(2):312.
[16]Bian, Y.; Liu, X.; Ji, K.; et al. Efficient Synthesis of Highly Substituted Pyrroles Based on the TandemReactions: Intermolecular Amination and Pd(II)-Catalyzed Intramolecular Hydroamidation[J].Tetrahedron,2009,65(7):1424.
[17]Cadierno, V.; Gimeno, J.; and Nebra, N.; One-Pot Three-Component Catalytic Synthesis of FullySubstituted Pyrroles from Readily Available Propargylic Alcohols,1,3-Dicarbonyl Compounds andPrimary Amines. Chem. Eur. J.2007,13,9973.
[18]Khalili, B.; Jajarmi, P.; Eftekhari-Sis, B.; and Hashemi, M.; M.; Novel One-Pot, Three-ComponentSynthesis of New2-Alkyl-5-aryl-(1H)-pyrrole-4-ol in Water. J. Org. Chem.2008,73,2090.
[19]Khlebnikov, A.; V. Golovkina, M.; S. Novikov, M.; and S. Yufit, D.; A Novel Strategy for the Synthesisof3-(N-Heteryl)pyrrole Derivatives. Org. Lett,2012,14(14):3768.
[20]Ramanathan, B.; Keith, A.; Armstrong, D.; and Odom, A.; L.; Pyrrole Syntheses Based onTitanium-Catalyzed Hydroamination of Diynes. Org. Lett.,2004,17(6):2957.
[21]Arcadi, A.; Rossi, E.; et al Synthesis of Functionalised Furans and Pyrroles through AnnulationReactions of4-Pentynones[J]. Tetrahedron,1998,54(50):15253.
[22]Zhao, Y.; L.; Di, C.; H.; et al.[3+2] Cycloaddition of Propargylamines and-Acylketene Dithioacetals:A Synthetic Strategy for Highly Substituted Pyrroles. Adv. Synth. Catal.2012,354,3545.