Questions tagged [stereoelectronics]
For questions where the reactivity/conformation of the molecule is defined/controlled by a specific orbital arrangement/alignment (for example the unusual conformation of sugars because of the anomeric effect). This tag cannot be the only tag on a question. Tags such as [conformation] and [torganic-chemistry] must also be applied.
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Why do the dipoles in dichloroethane point in opposite directions?
I understand why the dipoles would align in a polar solvent to maximise dipole-dipole interactions but wouldn't the replulsion due to like charges destabilise the molecule? Is it a MO effect instead? ...
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Are diffuse functions necessary for modeling unbound conjugated anions?
According to this paper, and contrary to popular belief, diffuse functions are far from being necessary for the calculation of the electron affinities of the polycyclic aromatic hydrocarbon(PAH)s, due ...
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Mechanism of three-membered lactone hydrolysis in base
I was reading up on the participation of neighboring functional groups and in the reaction below, I was wondering why hydroxide attacks the C–O bond instead of the carbonyl group of the lactone. ...
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Solvent shell collapse
In "advanced organic chemistry part A" book page:306&307 , the author uses the term 'solvent shell collapse' when talking about the reason for retention of conformation in tertiary ...
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A question about geometry of benzenetetrol
In the 3d conformation of 1,2,4,5 - benzenetetrol, how could i determine the direction to which hydrogen atoms of hydroxyl groups would point? and if there were tertiary butyl groups in positions 3 &...
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Why is a 7-endo radical cyclisation favoured over a 6-exo in this synthesis?
Normally, according to Baldwin's rules, 3-exo to 7-exo cyclisations are preferred over endo cyclisations. But in the following example, a 7-endo-trig reaction is favoured over a 6-exo-trig and I am ...
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Regioselectivity in iodolactonisation of γ,δ-unsaturated carboxylic acid
In the last step of the iodolactonisation of 3,3-dimethylpent-4-enoic acid,[1,2] why does the carboxylate attack the iodonium to form a 5-membered ring, when a more stable 6-membered ring is possible? ...
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Rationalising diastereoselectivity of hydroboration using stereoelectronics
Using bulky reagents such as 9-BBN, hydroboration is often highly diastereoselective, giving rise to the 1,2-anti diastereomer:
This is easily explained using a steric argument, with the major ...
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Why is 1-bromotriptycene inert to nucleophilic substitution?
According to my textbook, 1-bromotriptycene is inert to any nucleophilic substitutions.
Due to steric hinderance we can say SN2 reactions cannot occur, but I think SN1 reactions should be favoured as ...
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Why is methyl α-D-glucopyranoside preferentially formed from glucopyranose in acidic methanol?
According to my textbook Organic Chemistry 2e by David Klein, the formation of a glycoside from glucopyranose favors the α form (see picture below).
Why does this happen? Shouldn't the equilibrium ...
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Stereoelectronic effects in torquoselectivity of 4π electrocyclic opening
Thermal 4π electrocyclic ring openings of cyclobutenes to form butadienes are known to proceed in a conrotatory manner, consistent with the Woodward–Hoffmann rules. However, there are two different ...
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Stereoelectronics of the Houk model
In Clayden's Organic Chemistry it gives the Houk model as a way for predicting selectivity for alkene reactions where an existing stereocentre is present (diastereoselectivity).
Unlike the ...
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Stabilisation of carbocations through hyperconjugation
Our teachers told us that greater the number of alpha H, greater is the stability of carbocation.
But consider this:
$\ce{CH3CH2+}$ and. $\ce{CH3CH2CH2+}$
The first one has 3 alpha H ...
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lowest energy conformation of butan-2,4-diol
Do the OH groups want to be furthest apart? or the CH3 groups?
I'm trying to determine the lowest energy conformation - and I don't know which group has the bigger steric effect?
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Gauche effect and bond length
Which of the following compounds has the longest bond length?
(A) $\ce{H3C-CF3}$
(B) $\ce{FCH2-CH2F}$
(C) $\ce{F2CH-CHF2}$
(D) $\ce{F3C-CF3}$
My logic was based on the relative electronegativities of ...
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