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
CodeReview question markdown downloader
Could a robot that can survive at the center of the Earth also survive a nuclear explosion?
Why Roll20 gives me two results instead of one?
What license do I use when I don't want stock image companies charging people money for photos?
List Product / Combinations With Strings
How to permanently set refresh interval for top command?
How to arrange objects in outward facing circle?
Finding New York City tournaments as a visitor from Moscow
Is it possible to kill parasitic worms by intoxicating oneself?
What to do with excess co-ax cable
Marijuana use and job/grant opportunities
How can I get 2 characters to bond while standing alternate watches?
Planet where giant manned machines travel in convoy across surface, tracking some astronomical phenomenon
Why are the Democrats & Republicans so homogeneous in their opinions of impeaching Trump?
How can I show that a sphere is rolling in a simulation?
I've never seen this before. Is this primarily a "rote computational trick" for multiplication by 9 ...?
Eating Titan's oceans
Why aren't we seeing carbon taxes in practice?
How does the bypass air provide thrust?
Are there any spell casters that can cast life giving spells without 'expensive' components?
How to optimise the use of 10 nuclear fuel pellets in medieval period?
What is the narrative difference between a Charisma and Wisdom saving throw?
How to think about speed or velocity of an electron (in an atom)?
Software to assist drawing of complex, three-dimensional skeletal formula from scratch or from existing crystal structure
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;
$begingroup$
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.
organic-chemistry organic-reduction
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
$endgroup$
add a comment
|
$begingroup$
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.
organic-chemistry organic-reduction
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
$endgroup$
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
add a comment
|
$begingroup$
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.
organic-chemistry organic-reduction
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
$endgroup$
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
organic-chemistry organic-reduction
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
asked Oct 1 at 9:40
Tan Yong BoonTan Yong Boon
7,5691 gold badge19 silver badges60 bronze badges
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
add a comment
|
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
add a comment
|
1 Answer
1
active
oldest
votes
$begingroup$
Carbamates are usually reduced to N-methyl groups. There are numerous examples:
J. Am. Chem. Soc. 2012, 134 (16), 6936–6939
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:
Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
$endgroup$
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
add a comment
|
Your Answer
StackExchange.ready(function()
var channelOptions =
tags: "".split(" "),
id: "431"
;
initTagRenderer("".split(" "), "".split(" "), channelOptions);
StackExchange.using("externalEditor", function()
// Have to fire editor after snippets, if snippets enabled
if (StackExchange.settings.snippets.snippetsEnabled)
StackExchange.using("snippets", function()
createEditor();
);
else
createEditor();
);
function createEditor()
StackExchange.prepareEditor(
heartbeatType: 'answer',
autoActivateHeartbeat: false,
convertImagesToLinks: false,
noModals: true,
showLowRepImageUploadWarning: true,
reputationToPostImages: null,
bindNavPrevention: true,
postfix: "",
imageUploader:
brandingHtml: "Powered by u003ca class="icon-imgur-white" href="https://imgur.com/"u003eu003c/au003e",
contentPolicyHtml: "User contributions licensed under u003ca href="https://creativecommons.org/licenses/by-sa/4.0/"u003ecc by-sa 4.0 with attribution requiredu003c/au003e u003ca href="https://stackoverflow.com/legal/content-policy"u003e(content policy)u003c/au003e",
allowUrls: true
,
onDemand: true,
discardSelector: ".discard-answer"
,immediatelyShowMarkdownHelp:true
);
);
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f121917%2freduction-of-carbamate-with-lah%23new-answer', 'question_page');
);
Post as a guest
Required, but never shown
1 Answer
1
active
oldest
votes
1 Answer
1
active
oldest
votes
active
oldest
votes
active
oldest
votes
$begingroup$
Carbamates are usually reduced to N-methyl groups. There are numerous examples:
J. Am. Chem. Soc. 2012, 134 (16), 6936–6939
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:
Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
$endgroup$
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
add a comment
|
$begingroup$
Carbamates are usually reduced to N-methyl groups. There are numerous examples:
J. Am. Chem. Soc. 2012, 134 (16), 6936–6939
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:
Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
$endgroup$
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
add a comment
|
$begingroup$
Carbamates are usually reduced to N-methyl groups. There are numerous examples:
J. Am. Chem. Soc. 2012, 134 (16), 6936–6939
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:
Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
$endgroup$
Carbamates are usually reduced to N-methyl groups. There are numerous examples:
J. Am. Chem. Soc. 2012, 134 (16), 6936–6939
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:
Angew. Chem. Int. Ed. 2002, 41 (24), 4683–4685
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
answered Oct 1 at 10:46
orthocresol♦orthocresol
47.3k7 gold badges145 silver badges272 bronze badges
answered Oct 1 at 10:46
orthocresol♦orthocresol
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
add a comment
|
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
add a comment
|
Thanks for contributing an answer to Chemistry Stack Exchange!
- Please be sure to answer the question. Provide details and share your research!
But avoid …
- Asking for help, clarification, or responding to other answers.
- Making statements based on opinion; back them up with references or personal experience.
Use MathJax to format equations. MathJax reference.
To learn more, see our tips on writing great answers.
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f121917%2freduction-of-carbamate-with-lah%23new-answer', 'question_page');
);
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
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