Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia

Gunanathan, Chidambaram; Milstein, David

doi:10.1002/anie.200803229

Cited by 477 publications

(222 citation statements)

References 27 publications

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“…In general, such a process requires multi-step redox transformations (Scheme 1, a), although recent advances have realized the alcohol-amine transformation by the hydrogen-borrowinglending strategy in one pot without scaffold reorganization. [27] In addition, we expanded this strategy to the transformation from benzyl alcohol into another benzyl alcohol by replacing one aldehyde with another aldehyde through Rh-catalyzed C À C bond cleavage/nucleophilic addition (Scheme 1, b). Formally, this kind of transformation is a direct group substitution (displacement) reaction through cleavage of a C À C single bond (Scheme 1, c).…”

Section: Introductionmentioning

confidence: 99%

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl‐directed Rh‐catalyzed CC bond cleavage of secondary alcohols and subsequent addition to CX (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of CC bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in‐depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron‐rich alcohols and electron‐deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the CC bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The CC cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the CC cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of CC cleavage/nucleophilic addition and CC cleavage/protonation/CH activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the “group transplant”, this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.

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Section: Introductionmentioning

confidence: 99%

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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“…Until now, reports are largely focused on Ru- [5] or Ir- [6] based homogeneous systems, which are not practically useful because of the problem of reusability and/or the indispensable use of large amounts of additives or co-catalysts. Although there are several reports on the cross-coupling of amines and alcohols using heterogeneous catalysts, [7] most of them suffer from harsh reaction conditions, low turnover numbers (TONs) and frequencies (TOFs), limited substrate scope, and/or the use of excess alcohols/amines to achieve high yields.…”

mentioning

confidence: 99%

Efficient and Clean Gold‐Catalyzed One‐Pot Selective N‐Alkylation of Amines with Alcohols

Lou

Liu

et al. 2010

Chemistry A European J

167

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“…When the reaction of 1-butanol was prolonged to 48 h the yield of dibutylamine increased to 88 % while 1-butylamine completely disappeared, and 7 % of butyl butyrate were also formed ( Table 1, entry 2), indicating that complex 3 catalyzes the conversion of the initially formed primary amines to secondary amines under these conditions [14]. Exploring the scope of this reaction, various aliphatic primary alcohols were subjected to amination using 7 atm of NH 3 .…”

Section: Resultsmentioning

confidence: 99%

“…In 2008, we reported the first direct homogenous catalytic selective amination of primary alcohols to primary amines using ammonia [14]. Later, the research groups of Vogt [15] and Beller [16] developed methods for the conversion of secondary alcohols to primary amines with ammonia.…”

Section: Introductionmentioning

confidence: 99%

Direct Synthesis of Secondary Amines From Alcohols and Ammonia Catalyzed by a Ruthenium Pincer Complex

et al. 2014

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Efficient and selective direct synthesis of secondary amines from primary alcohols and ammonia with liberation of water has been achieved, with high turnover numbers and with no generation of waste. In case of benzylic alcohols, imines rather than amines are obtained. This atom economical, environmentally benign reaction is homogenously catalyzed by a well-defined bipyridine based Ru(II)-PNN pincer complex.

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Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia

Cited by 477 publications

References 27 publications

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Efficient and Clean Gold‐Catalyzed One‐Pot Selective N‐Alkylation of Amines with Alcohols

Direct Synthesis of Secondary Amines From Alcohols and Ammonia Catalyzed by a Ruthenium Pincer Complex

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