Reduction of carbamate with LAHKetone/aldehyde synthesis from N-acylazetidines or aziridinesHow can a ketone be enantioselectively reduced, in the presence of an ester?Reduction of glucose to hexane with hydroiodic acidReduction of nitro compound using protection groupReduction using sodium borohydrideReduction with NH2-NH2 , OH-, and glycolDiborane reduction

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Reduction of carbamate with LAH


Ketone/aldehyde synthesis from N-acylazetidines or aziridinesHow can a ketone be enantioselectively reduced, in the presence of an ester?Reduction of glucose to hexane with hydroiodic acidReduction of nitro compound using protection groupReduction using sodium borohydrideReduction with NH2-NH2 , OH-, and glycolDiborane reduction






.everyoneloves__top-leaderboard:empty,.everyoneloves__mid-leaderboard:empty,.everyoneloves__bot-mid-leaderboard:empty
margin-bottom:0;









7















$begingroup$


The products of the reduction of esters with $ce LiAlH4$ and the products of the reduction of amides with $ce LiAlH4$ are vastly different. The former reduction cleaves the ester and produces two alcohols while the latter reduction produces an amine with the carbonyl group of the original amide replaced with $ce CH2$. A carbamate seems to display both chemical behaviour of esters and amides. I am curious to know what would be the mechanism by which reduction of carbamate with $ce LiAlH4$ takes place and what would be the products of such a reduction.










share|improve this question









$endgroup$










  • 3




    $begingroup$
    Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
    $endgroup$
    – Waylander
    Oct 1 at 10:45


















7















$begingroup$


The products of the reduction of esters with $ce LiAlH4$ and the products of the reduction of amides with $ce LiAlH4$ are vastly different. The former reduction cleaves the ester and produces two alcohols while the latter reduction produces an amine with the carbonyl group of the original amide replaced with $ce CH2$. A carbamate seems to display both chemical behaviour of esters and amides. I am curious to know what would be the mechanism by which reduction of carbamate with $ce LiAlH4$ takes place and what would be the products of such a reduction.










share|improve this question









$endgroup$










  • 3




    $begingroup$
    Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
    $endgroup$
    – Waylander
    Oct 1 at 10:45














7













7









7





$begingroup$


The products of the reduction of esters with $ce LiAlH4$ and the products of the reduction of amides with $ce LiAlH4$ are vastly different. The former reduction cleaves the ester and produces two alcohols while the latter reduction produces an amine with the carbonyl group of the original amide replaced with $ce CH2$. A carbamate seems to display both chemical behaviour of esters and amides. I am curious to know what would be the mechanism by which reduction of carbamate with $ce LiAlH4$ takes place and what would be the products of such a reduction.










share|improve this question









$endgroup$




The products of the reduction of esters with $ce LiAlH4$ and the products of the reduction of amides with $ce LiAlH4$ are vastly different. The former reduction cleaves the ester and produces two alcohols while the latter reduction produces an amine with the carbonyl group of the original amide replaced with $ce CH2$. A carbamate seems to display both chemical behaviour of esters and amides. I am curious to know what would be the mechanism by which reduction of carbamate with $ce LiAlH4$ takes place and what would be the products of such a reduction.







organic-chemistry organic-reduction






share|improve this question













share|improve this question











share|improve this question




share|improve this question










asked Oct 1 at 9:40









Tan Yong BoonTan Yong Boon

7,5691 gold badge19 silver badges60 bronze badges




7,5691 gold badge19 silver badges60 bronze badges










  • 3




    $begingroup$
    Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
    $endgroup$
    – Waylander
    Oct 1 at 10:45













  • 3




    $begingroup$
    Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
    $endgroup$
    – Waylander
    Oct 1 at 10:45








3




3




$begingroup$
Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
$endgroup$
– Waylander
Oct 1 at 10:45





$begingroup$
Carbamate reduction with LiAlH4 gives N-methylation, see nrcresearchpress.com/doi/pdfplus/10.1139/v66-043 and Tet. Letts vol 26 (1985) 5367
$endgroup$
– Waylander
Oct 1 at 10:45











1 Answer
1






active

oldest

votes


















9

















$begingroup$

Carbamates are usually reduced to N-methyl groups. There are numerous examples:



Reduction of methyl carbamate



J. Am. Chem. Soc. 2012, 134 (16), 6936–6939



Reduction of t-butyl carbamate / Boc



Org. Lett. 2012, 14 (18), 4834–4837



But it is not always a given. In this next example, the nitrogen is part of a three-membered ring (aziridine). These nitrogens are better leaving groups than usual, cf. Ketone/aldehyde synthesis from N-acylazetidines or aziridines where the same kind of reactivity is observed:



Reduction of aziridine carbamate



Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685






share|improve this answer










$endgroup$









  • 1




    $begingroup$
    What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
    $endgroup$
    – Tan Yong Boon
    Oct 1 at 11:29






  • 1




    $begingroup$
    You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
    $endgroup$
    – orthocresol
    Oct 1 at 11:38







  • 2




    $begingroup$
    @orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
    $endgroup$
    – user55119
    Oct 1 at 22:42










  • $begingroup$
    @user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
    $endgroup$
    – orthocresol
    Oct 27 at 23:38













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1 Answer
1






active

oldest

votes








1 Answer
1






active

oldest

votes









active

oldest

votes






active

oldest

votes









9

















$begingroup$

Carbamates are usually reduced to N-methyl groups. There are numerous examples:



Reduction of methyl carbamate



J. Am. Chem. Soc. 2012, 134 (16), 6936–6939



Reduction of t-butyl carbamate / Boc



Org. Lett. 2012, 14 (18), 4834–4837



But it is not always a given. In this next example, the nitrogen is part of a three-membered ring (aziridine). These nitrogens are better leaving groups than usual, cf. Ketone/aldehyde synthesis from N-acylazetidines or aziridines where the same kind of reactivity is observed:



Reduction of aziridine carbamate



Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685






share|improve this answer










$endgroup$









  • 1




    $begingroup$
    What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
    $endgroup$
    – Tan Yong Boon
    Oct 1 at 11:29






  • 1




    $begingroup$
    You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
    $endgroup$
    – orthocresol
    Oct 1 at 11:38







  • 2




    $begingroup$
    @orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
    $endgroup$
    – user55119
    Oct 1 at 22:42










  • $begingroup$
    @user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
    $endgroup$
    – orthocresol
    Oct 27 at 23:38
















9

















$begingroup$

Carbamates are usually reduced to N-methyl groups. There are numerous examples:



Reduction of methyl carbamate



J. Am. Chem. Soc. 2012, 134 (16), 6936–6939



Reduction of t-butyl carbamate / Boc



Org. Lett. 2012, 14 (18), 4834–4837



But it is not always a given. In this next example, the nitrogen is part of a three-membered ring (aziridine). These nitrogens are better leaving groups than usual, cf. Ketone/aldehyde synthesis from N-acylazetidines or aziridines where the same kind of reactivity is observed:



Reduction of aziridine carbamate



Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685






share|improve this answer










$endgroup$









  • 1




    $begingroup$
    What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
    $endgroup$
    – Tan Yong Boon
    Oct 1 at 11:29






  • 1




    $begingroup$
    You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
    $endgroup$
    – orthocresol
    Oct 1 at 11:38







  • 2




    $begingroup$
    @orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
    $endgroup$
    – user55119
    Oct 1 at 22:42










  • $begingroup$
    @user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
    $endgroup$
    – orthocresol
    Oct 27 at 23:38














9















9











9







$begingroup$

Carbamates are usually reduced to N-methyl groups. There are numerous examples:



Reduction of methyl carbamate



J. Am. Chem. Soc. 2012, 134 (16), 6936–6939



Reduction of t-butyl carbamate / Boc



Org. Lett. 2012, 14 (18), 4834–4837



But it is not always a given. In this next example, the nitrogen is part of a three-membered ring (aziridine). These nitrogens are better leaving groups than usual, cf. Ketone/aldehyde synthesis from N-acylazetidines or aziridines where the same kind of reactivity is observed:



Reduction of aziridine carbamate



Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685






share|improve this answer










$endgroup$



Carbamates are usually reduced to N-methyl groups. There are numerous examples:



Reduction of methyl carbamate



J. Am. Chem. Soc. 2012, 134 (16), 6936–6939



Reduction of t-butyl carbamate / Boc



Org. Lett. 2012, 14 (18), 4834–4837



But it is not always a given. In this next example, the nitrogen is part of a three-membered ring (aziridine). These nitrogens are better leaving groups than usual, cf. Ketone/aldehyde synthesis from N-acylazetidines or aziridines where the same kind of reactivity is observed:



Reduction of aziridine carbamate



Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685







share|improve this answer













share|improve this answer




share|improve this answer










answered Oct 1 at 10:46









orthocresolorthocresol

47.3k7 gold badges145 silver badges272 bronze badges




47.3k7 gold badges145 silver badges272 bronze badges










  • 1




    $begingroup$
    What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
    $endgroup$
    – Tan Yong Boon
    Oct 1 at 11:29






  • 1




    $begingroup$
    You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
    $endgroup$
    – orthocresol
    Oct 1 at 11:38







  • 2




    $begingroup$
    @orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
    $endgroup$
    – user55119
    Oct 1 at 22:42










  • $begingroup$
    @user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
    $endgroup$
    – orthocresol
    Oct 27 at 23:38













  • 1




    $begingroup$
    What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
    $endgroup$
    – Tan Yong Boon
    Oct 1 at 11:29






  • 1




    $begingroup$
    You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
    $endgroup$
    – orthocresol
    Oct 1 at 11:38







  • 2




    $begingroup$
    @orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
    $endgroup$
    – user55119
    Oct 1 at 22:42










  • $begingroup$
    @user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
    $endgroup$
    – orthocresol
    Oct 27 at 23:38








1




1




$begingroup$
What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
$endgroup$
– Tan Yong Boon
Oct 1 at 11:29




$begingroup$
What if the "ester part" of the carbamate is also linked to another part of the molecule such that it doesn't simply go away after reduction? What would happen to the "ester part" of the carbamate upon reduction?
$endgroup$
– Tan Yong Boon
Oct 1 at 11:29




1




1




$begingroup$
You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
$endgroup$
– orthocresol
Oct 1 at 11:38





$begingroup$
You get the alcohol. e.g. N-CO2Et -> EtOH There aren't really other ways to link a carbamate to some other part of the molecule; the central carbon (which becomes the NMe carbon) has to have four bonds to either N or O. The N bit becomes NMe and the O bit becomes the alcohol.
$endgroup$
– orthocresol
Oct 1 at 11:38





2




2




$begingroup$
@orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
$endgroup$
– user55119
Oct 1 at 22:42




$begingroup$
@orthocresol: H. C. Brown, et al., argue that it is the inability of the aziridine to form the iminium structure that represses reductive alkylation in favor of aziridine formation. J.A.C.S, 1961, 83, 4549.
$endgroup$
– user55119
Oct 1 at 22:42












$begingroup$
@user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
$endgroup$
– orthocresol
Oct 27 at 23:38





$begingroup$
@user55119 thank you for the reference (I just noticed this). That is consistent with the rationale provided in the question I linked, which is good!
$endgroup$
– orthocresol
Oct 27 at 23:38



















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