Questions tagged [regioselectivity]
For questions involving selectivity as to where a functional group reacts.
76
questions
2
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62 views
Why do the induction effects of fluorobenzene decrease electrophilic addition reactivity, conjugation effects increase selectivity?
Fluorobenzene shows signs of both the electron withdrawing and electron donating groups on benzene. Electrophilic substitution to the ring is less reactive because the fluorine is very electronegative ...
2
votes
1answer
44 views
Bromohydration regioselectivity
In which of these cases would the addition of $\ce{Br2/H2O}$ be highly regioselective?
$$\ce{CH3CH=CHCH2CH3}$$ or $$\ce{(CH3)2C=CH2}$$
since both are asymmetric alkenes, how do I answer the question?...
4
votes
1answer
80 views
Stereochemical outcomes in opening of vinyl epoxides
Explain the outcomes of the following reactions. In each case the major product is shown.
Firstly, I don't understand why the chloride always attacks on the right hand side of the epoxide. Also,...
0
votes
1answer
96 views
Why is the major product of the reaction of 1-naphtol with benzene diazonium chloride not the ortho product?
If 1-napthol reacts with benzene diazonium chloride, it gives the para product with respect to the hydroxyl group. However, shouldn't the major product be the ortho one, because there will be ...
5
votes
1answer
128 views
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 ...
0
votes
0answers
39 views
What is the product when 1,4,6-trifluoroazulene is treated with sodium methoxide?
My logic
During substitution via Path 1 and Path 2 aromatic intermediates are formed.
Via path 3 anti aromatic intermediate is formed.
Therefore reaction takes place via path 1 and path 2 only.
...
13
votes
2answers
1k views
Does aniline react with diazonium ions at C or N?
In the azo coupling of aniline with benzenediazonium cation, I thought of two possible products 1 and 2 that could be formed. However, I can't work out which will be preferred. What would be the major ...
4
votes
2answers
110 views
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? ...
3
votes
1answer
145 views
How does base size affect the ratio of kinetic/thermodynamic enolate?
One of the factors that favor kinetic products is bulky bases. So, I'd expect that, for a certain substrate, the use of a more bulky base to favor even more the kinetic product.
However, in the table ...
3
votes
1answer
543 views
Why does nucleophilic aromatic substitution occur at C-2 and C-4 of pyridine?
In the following reaction of 2,3,4-tribromopyridine with sodium methoxide in methanol,[1] why are only the C-2 and C-4 bromines replaced with methoxy groups?
Why doesn't the bromine at C-3 also get ...
20
votes
1answer
494 views
Regioselectivity of epoxide hydrogenation using Pt versus Ni catalyst
What conditions are applicable for the transformations X and Y, respectively?
(a) $\ce{LiAlH4}$, and $\ce{NaBH4}$
(b) $\ce{NaBH4}$, and $\ce{BCl3}$ followed by $\ce{NaBH4}$
(c) $\ce{LiAlH4}$, ...
6
votes
2answers
368 views
Claisen rearrangement in substituted ring
This is an example of Claisen rearrangement, property of allyl vinyl/phenyl ethers.
I believe that the allylic migration should take place to the position ortho to both $\ce{-CH3}$ and $-\ce{OR}$ ...
7
votes
1answer
232 views
Selectivity in aldol condensation of 7-oxo(6,6-²H₂)octanal
I am supposed to find the product of the following reaction:
I know that six-membered rings are more stable than five-membered rings, but the C-D bonds are stronger, so it confuses me where will the ...
2
votes
0answers
435 views
Reactivity and selectivity in free radical halogenation of alkanes
I read about the free radical halogenation of alkanes with $\ce{X2}$ and I have the following questions:
Given that the first step is the homolytic breaking of the $\ce{X-X}$ bond, and the homolytic ...
8
votes
2answers
408 views
How does Hofmann elimination work in this reaction?
In my Chemistry class, we were given this question to solve, and I'm not sure I fully understood the solution.
I understand that since the substrate is bulky, Saytzeff elimination can't happen, so it ...
1
vote
1answer
4k views
Why does radical chlorination and bromination of propane occur at different positions?
When propane reacts with chlorine, we will mostly (theoretically) get an isomer with a chlorine on the end. ($\ce{CH_3-CH_2-CH_2Cl}$). However, when propane reacts with bromine, we will mostly get an ...
11
votes
1answer
293 views
Most activated position on para-terphenyl for EAS
Para-terphenyl: it doesn't look pretty with all those math-y numbers, but those are going to come helpful in answering my question!
A question asked me to tell the expected product when this reacts ...
4
votes
1answer
410 views
Regioselectivity in Claisen condensation and aldol reaction
I'm having a hard time determining regio-selectivity in those two reactions.
At the image above I've drawn one example for each on of them. My question is how do we choose where the deprotonation ...
7
votes
0answers
67 views
How can organocuprates generated with catalytic Cu(I) be competitive in 1,4-addition to an enone?
Organocopper compounds (e.g. $\ce{LiCuR_2}$) are often prepared from an organolithium or Grignard reagent when a soften nucleophile is needed, such as for a conjugate addition to an $\alpha,\beta$-...
5
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0answers
539 views
Why do t-butyl bromide and silver(I) nitrite form the nitroalkane, not the nitrite ester?
We know that reaction of $\ce{AgNO2}$ with alkyl halides is SN1 type reaction and follows HSAB principle. So in the reaction of $\ce{(CH3)3C Br}$ we would expect $\ce{AgBr}$ to form and also a ...
4
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0answers
194 views
Stability of extended enolates
I'd expect an extended enolate to be more stable than a normal enolate, when both can form, but my textbook suggests otherwise.
What is the stability of an extended enolate compared with a normal ...
5
votes
1answer
4k views
Why does LiAlH4 reduce the double bond of cinnamaldehyde, whereas NaBH4 does not?
I read an answer here about why $\ce{LiAlH_4}$ does not reduce conjugated double bonds, and that $\ce{NaBH_4}$ does. But in the case of cinnamaldehyde, $\ce{LiAlH_4}$ reduces the conjugated double ...
3
votes
0answers
104 views
Regioselectivity in the aldolcondensation towards (Z)-Jasmon
In the synthesis of (Z)-Jasmone via aldol-condensation as shown below,
how can the observed regioselectivity be explained?
After all, it is also possible to form the side product shown below. I ...
0
votes
1answer
85 views
Deciding which α-Η gets abstracted in aldol condensation
Consider the base catalysed aldol condensation of methyl ethyl ketone. The first step involves the abstraction of a proton by the base. However I am having trouble deciding whether the proton will be ...
1
vote
1answer
349 views
Carbocation formation in electrophilic addition of hydrogen halides to alkenes
Question:
My attempt:
I made the carbocation on the carbon labelled $1$ because I think that the positive charge would be slightly more stable on $1$ compared to $2$ due to the inductive effect of $\...
0
votes
1answer
264 views
Nonsubstituted Cycloalkene HBr Reaction
If I have a cyclohexene with no substituents and add HBr, how do I know what side of the former double bond to place the Br anion? I think I understand Markovnikov's rule, but in my chemistry book ...
-2
votes
1answer
445 views
Why is isopropylbromide formed as the major product but not n-propylbromide from 1-propene?
When 1-propane reacts with HBr, the major product formed is isopropyl bromide and minor product is n-propyl bromide. I know that this is said to happen because the reaction mechanism favours the ...
6
votes
0answers
515 views
Why does phenol react on oxygen in the Gattermann–Koch reaction?
When discussing the Gattermann–Koch reaction on phenol substrates, it has been said that O-acylation is a problematic competing reaction as
in a phenol, there's high electron density on the O atom [...
2
votes
1answer
81 views
Separation of alkylated 1,2,4-triazole in solution
I was looking into heterocyclic compounds and their alkylation (i.e. the regioselectivity of the alkylation of the compound).
People are able to give pretty exact numbers, for an experiment done in ...
7
votes
1answer
587 views
Nucleophilic aromatic substitution on pyrimidines: C2 vs C4 selectivity
[There are many similar questions on Chemistry.SE (e.g. 1, 2) and a quick search will reveal all of them, but nothing on this in particular.]
The reaction of 2,4-halopyrimidines with nucleophiles ...
13
votes
1answer
183 views
Ring opening of aziridinylmethyl and oxiranylmethyl radicals
When a radical is alpha to a three-membered ring, it is common for the ring to open via β-scission (to relieve ring strain):
When the ring contains a heteroatom there are a couple of different ...
2
votes
1answer
307 views
Selectivity in acetonide formation from a polyol
In my total synthesis lecture notes the above example is given in which a polyol is reacted under acetonide forming conditions.
The notes point out that this product is the only product, no other ...
10
votes
1answer
217 views
Why is nitrosobenzene electrophilic on O in organocatalytic oxygenations?
In 2003 Zhong1 and MacMillan2 reported the use of nitrosobenzene, PhNO, in the organocatalytic asymmetric α-oxygenation of carbonyl compounds:
which is all nice, except for the slightly ...
8
votes
0answers
266 views
Sulfonyl azides: diazo or azide transfer?
Sulfonyl azides, $\ce{RSO2N3}$, are capable of acting as sources of electrophilic azide ("$\ce{N+3}$"), but are also capable of effecting diazo transfer, as shown in the scheme below, taken from ref 1:...
3
votes
1answer
2k views
Regioselectivity in Friedel–Crafts acylation of thiophene
In the above reaction, I understand that $\ce{AlCl3}$ is acting as a Lewis acid to generate an acylium ion, which is a strong electrophile.
Would this electrophile attack at carbon 2 or 3?
I think ...
0
votes
1answer
670 views
Regioselectivity in addition of hydrogen iodide to vinyl chloride
I encountered a question which was stated as:
The reaction of vinyl chloride with hydrogen iodide to give 1-chloro-1-iodoethane is an example of anti-Markovnikov addition. Is this true or false?
...
5
votes
1answer
82 views
Regioselectivity in opening of cationic three-membered rings
The mechanism of electrophilic addition on alkenes often involves an electrophile attacking the double bond and causing an electromeric shift of electrons. The electrophile then forms a bridged cation ...
2
votes
1answer
525 views
How is the acetoxy group ortho/para-directing in electrophilic aromatic substitution?
Why is the $\ce{-OAc}$ group o,p-directing in electrophilic aromatic substitution?
How can I compare the activating effect of $\ce{-OAc}$ with $\ce{-OH}$ and $\ce{O-}$? Is it to do with the number of ...
10
votes
1answer
229 views
Regioselectivity of an amination reaction of 2,6-dichloro-3-nitropyridine
In the formation of ethyl 4-(6-chloro-3-nitropyridin-2-yl)piperazine-1-carboxylate G, why is the substitution favoured at the 2-position? I would have said that the 6-position substitution is ...
8
votes
1answer
724 views
Why does boron add to the less substituted carbon in the hydroboration of an alkene?
In the hydroboration of a typical alkene, the boron fragment ends up attached to the less substituted carbon:
What are the electronic or steric factors that lead to this regioselectivity?
7
votes
1answer
98 views
Regioselectivity in the formation of an imidazo[1,2-a]pyrimidine
In the heterocycle synthesis below (taken from Org. Process Res. Dev. 2006, 10 (3), 398–402), a 5,6-fused heterocycle (an imidazo[1,2-a]pyrimidine) is formed by treating 2-amino-4-(trifluoromethyl)...
6
votes
1answer
2k views
Reaction of propylene oxide with ammonia or hydrazoic acid
I am supposed to identify the products A and B in the following scheme:
The three options I have been given are:
I think that since $\ce{HN3}$ is a stronger nucleophile than $\ce{NH3}$, B should ...
11
votes
1answer
526 views
Why do Grignard reagents add to propargyl alcohols?
In Phil Baran's lectures on heterocyclic chemistry at Scripps, one of the lecture problems is concerned with this synthesis of Vioxx:
The first step supposedly involves an anti addition of the aryl ...
0
votes
1answer
401 views
Why does sulfonation of aniline occur para rather than ortho?
According to a textbook by K. L. Chugh:
Sulfonation [of aniline] is a reversible reaction. The p-isomer, being more stable, does not get desulfonated easily. Hence, p-sulfanilic acid is the major ...
4
votes
2answers
778 views
What determines the high degree of selectivity in free radical brominations?
In my organic chemistry class, we were asked what determines the relatively high degree of selectivity in the reaction of a bromine radical with primary, secondary, and tertiary C–H bonds.
I said it ...
4
votes
2answers
241 views
Regioselectivity of deprotonation of 1,4-dicarbonyl
In the intramolecular aldol condensation of hexane-2,4-dione (above), why does the base abstract one of the $\ce{-CH3}$ protons instead of one of the $\ce{-CH2}$ protons? Both sets of protons are α to ...
24
votes
1answer
21k views
Addition of hydrogen bromide to 1,3-butadiene: thermodynamic and kinetic control
The reaction of one equivalent of hydrogen bromide with 1,3-butadiene gives different products at under different conditions:1
The addition of hydrogen chloride also gives rise to similar products.2 ...
20
votes
3answers
6k views
Why do SN2 reactions of alkyl halides proceed differently with KCN and AgCN?
Alkyl halides react with $\ce{KCN}$ to form alkyl cyanides as the main product, whereas the use of $\ce{AgCN}$ leads to isocyanides as the chief product. Why does this happen?
4
votes
0answers
279 views
Regioselectivity of the Beckmann rearrangement
It seems to be that the Beckmann rearrangement is a nice way to prepare secondary amines. This can be achieved by removal of oxygen via the use of $\ce{HI}$/$\ce{P}$. However, if ketones are used, ...
3
votes
2answers
20k views
Why can toluene be chlorinated at either the benzylic position or the ring depending on the conditions?
My book mentions a reaction for the preparation of benzaldehyde with toluene in which side chain chlorination of toluene gives (dichloromethyl)benzene, which upon hydrolysis gives benzaldehyde:
Why ...
