Steric and Stereoelectronic Effects in Organic Chemistry最新文献

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A Computational Study of the Relative Aromaticity of Pyrrole, Furan, Thiophene and Selenophene, and Their Diels-Alder Stereoselectivity 吡咯、呋喃、噻吩和硒烯的相对芳香性及其双醛立体选择性的计算研究
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 2020-07-30 DOI: 10.26434/chemrxiv.12734039
V. Yadav
{"title":"A Computational Study of the Relative Aromaticity of Pyrrole, Furan, Thiophene and Selenophene, and Their Diels-Alder Stereoselectivity","authors":"V. Yadav","doi":"10.26434/chemrxiv.12734039","DOIUrl":"https://doi.org/10.26434/chemrxiv.12734039","url":null,"abstract":"The collinearity of terminal p\u0000orbitals of a diene with that of a dienophile is required for an effective\u0000overlap to result in s bond formation during the Diels-Alder reaction.\u0000The ease of the DA reaction of a cyclic diene with a given dienophile,\u0000therefore, must also depend on the distance between the termini of the diene. A\u0000distance larger than the unsaturated bond of the dienophile is expected to\u0000raise the energy of activation. This scenario has been amply demonstrated from\u0000the study of reactions of several dienes, some designed to serve the purpose,\u0000with different dienophiles. The five-ring heterocycles pyrrole, furan,\u0000thiophene and selenophene possess varying aromatic character for the varied resonance\u0000participation of the heteroatom lone pair with ring p bonds. The aromaticity\u0000decreases in the same order due to: (a) the increasing sC-X (X = heteroatom) bond\u0000length lifts the bond uniformity required for ring current, hence aromaticity, such\u0000as in benzene and (b) size-mismatch of the interacting lone pair orbital and\u0000the ring p orbitals, especially in\u0000thiophene and selenophene, both allowing poor overlap in the ground state\u0000structures. It is demonstrated that increase alone in the activation energies\u0000of the DA reactions of pyrrole, furan, thiophene and selenophene cannot be considered\u0000a measure of relative aromaticity as often done and even theoretically attempted\u0000in many ways to prove just that. The separation of the termini of the diene has\u0000a much larger role in the determination of activation energy, especially in\u0000thiophene and selenophene, than their aromaticity profile. There cannot be a\u0000measure better than the relative intensity of heteroatom lone pair overlap with\u0000ring p bonds, giving rise to a six-electron like\u0000system in following Hückel’s 4n+2 rule, to assess the relative aromaticity.","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"48 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2020-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"129639990","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}
引用次数: 0
Steric and Stereoelectronic Effects in Organic Chemistry 有机化学中的立体电子和立体电子效应
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 2016-06-07 DOI: 10.1007/978-981-10-1139-9
V. Yadav
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引用次数: 9
Diastereoselectivity in Organic Reactions 有机反应中的非对映选择性
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-981-10-1139-9_3
V. Yadav
{"title":"Diastereoselectivity in Organic Reactions","authors":"V. Yadav","doi":"10.1007/978-981-10-1139-9_3","DOIUrl":"https://doi.org/10.1007/978-981-10-1139-9_3","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"20 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"121699446","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}
引用次数: 0
Steric and Stereoelectronic Control of Molecular Structures and Organic Reactions 分子结构和有机反应的立体电子控制
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2_1
V. Yadav
{"title":"Steric and Stereoelectronic Control of Molecular Structures and Organic Reactions","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2_1","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2_1","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"48 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"133227652","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}
引用次数: 0
The Overlap Component of the Stereoelectronic Effect vis-à-vis the Conservation of Orbital Symmetry Rules 立体电子效应的重叠分量与-à-vis轨道对称规则的守恒
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2_6
V. Yadav
{"title":"The Overlap Component of the Stereoelectronic Effect vis-à-vis the Conservation of Orbital Symmetry Rules","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2_6","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2_6","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"105 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"124868683","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}
引用次数: 0
Steric and Stereoelectronic Effects in Organic Chemistry 有机化学中的立体电子和立体电子效应
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2
V. Yadav
{"title":"Steric and Stereoelectronic Effects in Organic Chemistry","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"21 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"122640977","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}
引用次数: 2
The Conservation of Orbital Symmetry Rules (Woodward–Hoffmann Rules) 轨道对称守恒规则(Woodward-Hoffmann规则)
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2_5
V. Yadav
{"title":"The Conservation of Orbital Symmetry Rules (Woodward–Hoffmann Rules)","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2_5","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2_5","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"11 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"128958874","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}
引用次数: 0
Hammett Substituent Constants 哈米特取代基常数
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2_8
V. Yadav
{"title":"Hammett Substituent Constants","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2_8","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2_8","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"25 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"124975701","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}
引用次数: 1
Reactions on Saturated and Unsaturated Carbons 饱和碳和不饱和碳的反应
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-3-030-75622-2_2
V. Yadav
{"title":"Reactions on Saturated and Unsaturated Carbons","authors":"V. Yadav","doi":"10.1007/978-3-030-75622-2_2","DOIUrl":"https://doi.org/10.1007/978-3-030-75622-2_2","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"33 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"114664739","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}
引用次数: 0
A(1,2) and A(1,3) Strains A(1,2)和A(1,3)菌株
Steric and Stereoelectronic Effects in Organic Chemistry Pub Date : 1900-01-01 DOI: 10.1007/978-981-10-1139-9_4
V. Yadav
{"title":"A(1,2) and A(1,3) Strains","authors":"V. Yadav","doi":"10.1007/978-981-10-1139-9_4","DOIUrl":"https://doi.org/10.1007/978-981-10-1139-9_4","url":null,"abstract":"","PeriodicalId":447840,"journal":{"name":"Steric and Stereoelectronic Effects in Organic Chemistry","volume":"60 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"121073745","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}
引用次数: 1
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