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Volumn 14, Issue 5, 2008, Pages 1452-1463

Assessable consequences of through-bond donor-acceptor interactions in β-aminoketones

Author keywords

Donor acceptor systems; Hyperconjugation; Reactivity; Strained molecules; Through bond interactions

Indexed keywords

ABSORPTION; ESTERS; FLOW INTERACTIONS; ORGANIC COMPOUNDS; STRUCTURAL ANALYSIS;

EID: 43149087226     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200701220     Document Type: Article
Times cited : (10)

References (109)
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    • This nomenclature designates the amine (lone pair, n orbital) as the donor and the carbonyl (π* orbital) as the acceptor, although the orbital interactions are even more complex e.g. n → σ* c.c, σ →*c-o, etc
    • c-o, etc.).
  • 28
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    • Notably, treatment of triester-functionalized phloroglucinol derivatives with Lewis or prolic acids results, under certain condilions, in significant lactone formation. We are exploring this chemistry separately and will report on it in due course
    • Notably, treatment of triester-functionalized phloroglucinol derivatives with Lewis or prolic acids results, under certain condilions, in significant lactone formation. We are exploring this chemistry separately and will report on it in due course.
  • 29
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    • See a special issue on diastereoselectivity: a
    • See a special issue on diastereoselectivity: a) A. S. Cieplak. Chem. Rev. 1999, 99, 1265-1336;
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    • e) B. W. Gung, Chem. Rev. 1999, 99, 1377-1386;
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    • c) B. W. Gung. Tetrahedron 1996, 52, 5263-5301;
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    • b) Y. Senda, Chirality 2002, 14, 110-120.
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    • When the cyclization is performed in methanol, lhe triisopropyl ester (20, is obtained in addition to two of the three possible methyl ester derivatives the mono, 21, and bis-methylesler. 6
    • When the cyclization is performed in methanol, lhe triisopropyl ester (20%) is obtained in addition to two of the three possible methyl ester derivatives (the mono-, 21%, and bis-methylesler. 6 %)."
  • 56
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    • Compared with similar isopropyl ester substituents in the CSD (HEFKOS10= 1.508Å; HEFKUY10= 1.509 Å).
    • Compared with similar isopropyl ester substituents in the CSD (HEFKOS10= 1.508Å; HEFKUY10= 1.509 Å).
  • 58
    • 53849108813 scopus 로고    scopus 로고
    • The X-ray structures of 6 and 7 have been collected at 173 K, while those taken from the literature for comparison have generally been collected at room temperature (290-295 K). The consequence of temperature on through-bond interactions in these systems (in the solid state) is not known.
    • The X-ray structures of 6 and 7 have been collected at 173 K, while those taken from the literature for comparison have generally been collected at room temperature (290-295 K). The consequence of temperature on through-bond interactions in these systems (in the solid state) is not known.
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    • Side-by-side analysis of some structures is complicated by substitution a to the nitrogen, although comparison to similarly substituted aza-adamantanes suggests that the substituents should have a marginal effect on the bond lengths and angles of the core. Reference [24] stales for 23 thai the deformation of the tricyclic system induced by the incorporation of lhe phenyl ring is quite small.
    • Side-by-side analysis of some structures is complicated by substitution a to the nitrogen, although comparison to similarly substituted aza-adamantanes suggests that the substituents should have a marginal effect on the bond lengths and angles of the core. Reference [24] stales for 23 thai "the deformation of the tricyclic system induced by the incorporation of lhe phenyl ring is quite small."
  • 72
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    • V. Galasso, THEOCHEM 2000, 528, 171-176.
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    • Worth noting. DFT-LDA/cc-pVDZ calculations already performed on 4 (and reported in ref. [7c]) show bond lengths and angles for the AAT core that agree very well with those reported herein (generally within 0.01 Åand 1.5°. respectively). Calculations al the molecular mechanics level (e.g. Amber* force field) do not reproduce the bond length changes, a phenomenon noted in ref. [31e] but argued against in ref. [31 f].
    • Worth noting. DFT-LDA/cc-pVDZ calculations already performed on 4 (and reported in ref. [7c]) show bond lengths and angles for the AAT core that agree very well with those reported herein (generally within 0.01 Åand 1.5°. respectively). Calculations al the molecular mechanics level (e.g. Amber* force field) do not reproduce the bond length changes, a phenomenon noted in ref. [31e] but argued against in ref. [31 f].
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    • The n-π* transition is too weak to be observed in these systems see related results in ref, 5d
    • The n-π* transition is too weak to be observed in these systems (see related results in ref. [5d]).
  • 78
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    • This is not the case for through-bond interactions that show marked charge-transfer character. See, for example, ref, 19
    • This is not the case for through-bond interactions that show marked charge-transfer character. See, for example, ref. [19].
  • 79
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    • Cooperative stretching of the carbonyls in these systems has been noted before see below, ref, 43a, but we could not find any references of a comprehensive study or discussion
    • Cooperative stretching of the carbonyls in these systems has been noted before (see below, ref. [43a]). but we could not find any references of a comprehensive study or discussion.
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    • a) N. Risch, Chem. Ber. 1985, 118, 4849-4856;
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    • The average value for 1-aza-adamantanediones from ref. [43a] is δ ≈ 207 ppm. Such an NMR comparison of course depends significantly on how the chemical shifts are referenced (as well as other parameters).
    • The average value for 1-aza-adamantanediones from ref. [43a] is δ ≈ 207 ppm. Such an NMR comparison of course depends significantly on how the chemical shifts are referenced (as well as other parameters).
  • 92
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    • The latter two reagents oxidize diaza-adamantanones: see ref, 5d
    • The latter two reagents oxidize diaza-adamantanones: see ref. [5d].
  • 101
  • 105
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    • 3J(H.H) ≈ 12 Hz.
    • 3J(H.H) ≈ 12 Hz.
  • 107
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    • Bruker-AXS. Madison, Wisconsin, USA
    • SHELXTL6, Bruker-AXS. Madison, Wisconsin, USA, 2000.
    • (2000) SHELXTL6


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.