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For excellent leading references on hyperconjugation see: a
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11
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53849102585
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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
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c-o, etc.).
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28
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53849123331
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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.
-
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48
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53849148614
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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 %)."
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53849126848
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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).
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53849108813
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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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53849125441
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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."
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53849107488
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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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77
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53849140443
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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
-
-
53849097345
-
-
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
-
-
53849113980
-
-
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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80
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0021372290
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