7H-Naphth[3,2,1-cd]azulen-7-ones are synthesized by the intramolecular Friedel–Crafts cyclization of diethyl 4-phenylazulene-1,3-dicarboxylate derivatives with polyphosphoric acid (PPA). Treatment of 7H-naphth[3,2,1-cd]azulen-7-one with methyl trifluoromethanesulfonate or perchloric acid gives 7-methoxynaphth[3,2,1-cd]azulenium trifluoromethanesulfonate or 7-hydroxynaphth[3,2,1-cd]azulenium perchlorate. Both spectroscopic inspection and molecular orbital calculations for 7-hydroxynaphth[3,2,1-cd]azulenium ion show that the tropylium moiety is a main contributor to the ground state in the resonance structure. The syntheses of 7H-azuleno[1,8-bc]phenanthren-7-ones and 5,7-dihydrodinaphth[3,2,1-cd:1′,2′,3′-ij]azulene-5,7-diones are also described.
{"title":"Synthesis and some properties of 7H-naphth[3,2,1-cd]azulen-7-ones and related compounds","authors":"N. Abe, Hiroyuki Fujii, K. Takase, T. Morita","doi":"10.1039/B101333P","DOIUrl":"https://doi.org/10.1039/B101333P","url":null,"abstract":"7H-Naphth[3,2,1-cd]azulen-7-ones are synthesized by the intramolecular Friedel–Crafts cyclization of diethyl 4-phenylazulene-1,3-dicarboxylate derivatives with polyphosphoric acid (PPA). Treatment of 7H-naphth[3,2,1-cd]azulen-7-one with methyl trifluoromethanesulfonate or perchloric acid gives 7-methoxynaphth[3,2,1-cd]azulenium trifluoromethanesulfonate or 7-hydroxynaphth[3,2,1-cd]azulenium perchlorate. Both spectroscopic inspection and molecular orbital calculations for 7-hydroxynaphth[3,2,1-cd]azulenium ion show that the tropylium moiety is a main contributor to the ground state in the resonance structure. The syntheses of 7H-azuleno[1,8-bc]phenanthren-7-ones and 5,7-dihydrodinaphth[3,2,1-cd:1′,2′,3′-ij]azulene-5,7-diones are also described.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"373 1","pages":"1353-1358"},"PeriodicalIF":0.0,"publicationDate":"2010-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75799118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalytic asymmetric processes","authors":"Heather Tye, P. Comina","doi":"10.1039/A900862D","DOIUrl":"https://doi.org/10.1039/A900862D","url":null,"abstract":"","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"23 1","pages":"1729-1747"},"PeriodicalIF":0.0,"publicationDate":"2010-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82656327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Saturated oxygen heterocycles","authors":"M. Elliott","doi":"10.1039/A903885J","DOIUrl":"https://doi.org/10.1039/A903885J","url":null,"abstract":"Covering: 1 April 1998 to 30 June 1999. Previous review: J. Chem. Soc., Perkin Trans. 1, 1998, 4175.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"28 1","pages":"4175-4200"},"PeriodicalIF":0.0,"publicationDate":"2010-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73045524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Supported catalysts and their applications in synthetic organic chemistry","authors":"Y. R. Miguel, E. Brulé, Robert G. Margue","doi":"10.1039/B101948L","DOIUrl":"https://doi.org/10.1039/B101948L","url":null,"abstract":"","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"44 1","pages":"3085-3094"},"PeriodicalIF":0.0,"publicationDate":"2010-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73123732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Applications of stoichiometric transition metal complexes in organic synthesis","authors":"A. J. Fletcher, S. Christie","doi":"10.1039/B002281K","DOIUrl":"https://doi.org/10.1039/B002281K","url":null,"abstract":"","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"174 2","pages":"1-13"},"PeriodicalIF":0.0,"publicationDate":"2010-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91461562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of heterocycles by radical cyclisation","authors":"W. Russell Bowman, Colin F. Bridge, P. Brookes","doi":"10.1039/B108582B","DOIUrl":"https://doi.org/10.1039/B108582B","url":null,"abstract":"Covering: July 1998 to June 2000. Previous review: J. Chem. Soc., Perkin Trans. 1, 2000, 1.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"48 1","pages":"2747-2762"},"PeriodicalIF":0.0,"publicationDate":"2003-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89132650","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Rapid analogue syntheses of heteroaromatic compounds","authors":"I. Collins","doi":"10.1039/B108580H","DOIUrl":"https://doi.org/10.1039/B108580H","url":null,"abstract":"","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"56 1","pages":"1921-1940"},"PeriodicalIF":0.0,"publicationDate":"2003-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80108011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aza-[2,3]-Wittig rearrangement precursors derived from alanine, valine, phenylalanine and phenylglycine were synthesised with diethylamide and methylester anion stabilising groups. In the amide series only the alanine derived precursor rearranged upon deprotonation with KH. In the ester series the alanine, valine and phenylalanine precursors rearranged successfully with KH. The phenylalanine ester precursor gave an unselective rearrangement whereas rearrangement of the alanine and valine ester precursors gave levels and sense of diastereoselectivity in line with our transition state model. The products are chiral α,α-disubstituted-α-amino acid derivatives possessing two adjacent stereocentres and a vinyl silane synthetic handle.
{"title":"Synthesis of α,α-disubstituted unnatural amino acid derivatives using the aza-[2,3]-Wittig sigmatropic rearrangement","authors":"James C. Anderson, S. Skerratt","doi":"10.1039/B207295E","DOIUrl":"https://doi.org/10.1039/B207295E","url":null,"abstract":"Aza-[2,3]-Wittig rearrangement precursors derived from alanine, valine, phenylalanine and phenylglycine were synthesised with diethylamide and methylester anion stabilising groups. In the amide series only the alanine derived precursor rearranged upon deprotonation with KH. In the ester series the alanine, valine and phenylalanine precursors rearranged successfully with KH. The phenylalanine ester precursor gave an unselective rearrangement whereas rearrangement of the alanine and valine ester precursors gave levels and sense of diastereoselectivity in line with our transition state model. The products are chiral α,α-disubstituted-α-amino acid derivatives possessing two adjacent stereocentres and a vinyl silane synthetic handle.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"1 1","pages":"2871-2879"},"PeriodicalIF":0.0,"publicationDate":"2002-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89768549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Grignard reaction of perbenzylated β-cyclodextrin derivatives containing one 6-aldehydo group, or two 6-aldehydo groups in the A and D rings, was investigated. The reaction gave the stereoisomeric secondary alcohols expected for 1,2-addition in diastereomeric ratios of about 1 ∶ 3 ratio for the 6R- and 6S-isomers. Surprisingly the 6R-isomers were consistently found to be much less polar in terms of chromatographic retention times than the 6S-isomers. The polarity difference, which disappeared upon acetylation or oxidation, was interpreted as being caused by the presence or absence of intramolecular hydrogen bonding. This was supported by their IR spectra. The configurations of the diastereomers were determined by hydrolysis of the cyclodextrin and comparison of the modified glucose residues with reference compounds. Modelling studies suggest that 6-C-alkylation restricts the conformation around the C5–C6 bond such that the 6S-isomer will adopt a gg conformation, which has the hydroxy group pointing outwards, while the 6R-isomer will adopt a gt conformation, which has the OH group pointing towards the inner face of the cyclodextrin.
研究了含1个6-醛基团或A环和D环含2个6-醛基团的过苄基化β-环糊精衍生物的格氏反应。6R-和6s -异构体的非对映比约为1∶3，该反应可生成1,2-加成的立体异构仲醇。令人惊讶的是，在色谱保留时间方面，6r -异构体的极性一直比6s -异构体要小得多。极性差异在乙酰化或氧化后消失，被解释为是由分子内氢键的存在或不存在引起的。它们的红外光谱证实了这一点。通过环糊精的水解和修饰后的葡萄糖残基与参比化合物的比较，确定了非对映体的构型。模型研究表明，6- c -烷基化限制了C5-C6键周围的构象，使得6s -异构体将采用gg构象，羟基指向外，而6r -异构体将采用gt构象，羟基指向环糊精的内面。
{"title":"Unusual hydrogen-bonding differences in stereoisomeric 6-C-alkylated cyclodextrins","authors":"T. Hardlei, M. Bols","doi":"10.1039/B207033M","DOIUrl":"https://doi.org/10.1039/B207033M","url":null,"abstract":"The Grignard reaction of perbenzylated β-cyclodextrin derivatives containing one 6-aldehydo group, or two 6-aldehydo groups in the A and D rings, was investigated. The reaction gave the stereoisomeric secondary alcohols expected for 1,2-addition in diastereomeric ratios of about 1 ∶ 3 ratio for the 6R- and 6S-isomers. Surprisingly the 6R-isomers were consistently found to be much less polar in terms of chromatographic retention times than the 6S-isomers. The polarity difference, which disappeared upon acetylation or oxidation, was interpreted as being caused by the presence or absence of intramolecular hydrogen bonding. This was supported by their IR spectra. The configurations of the diastereomers were determined by hydrolysis of the cyclodextrin and comparison of the modified glucose residues with reference compounds. Modelling studies suggest that 6-C-alkylation restricts the conformation around the C5–C6 bond such that the 6S-isomer will adopt a gg conformation, which has the hydroxy group pointing outwards, while the 6R-isomer will adopt a gt conformation, which has the OH group pointing towards the inner face of the cyclodextrin.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"47 1","pages":"2880-2885"},"PeriodicalIF":0.0,"publicationDate":"2002-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74207974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
P. Page, Steven M. Allin, S. Maddocks, M. Elsegood
The development of several aziridine-based ligands for the asymmetric addition of diethylzinc to a selection of aromatic aldehydes is described. Positive nonlinear effects were observed, and shown to display substrate dependency.
{"title":"New ligands for asymmetric diethylzinc additions to aromatic aldehydes, demonstrating substrate-dependent nonlinear effects","authors":"P. Page, Steven M. Allin, S. Maddocks, M. Elsegood","doi":"10.1039/B208810J","DOIUrl":"https://doi.org/10.1039/B208810J","url":null,"abstract":"The development of several aziridine-based ligands for the asymmetric addition of diethylzinc to a selection of aromatic aldehydes is described. Positive nonlinear effects were observed, and shown to display substrate dependency.","PeriodicalId":17267,"journal":{"name":"Journal of The Chemical Society-perkin Transactions 1","volume":"12 1","pages":"2827-2832"},"PeriodicalIF":0.0,"publicationDate":"2002-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74427515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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