CDI-mediated monoacylation of symmetrical diamines and selective acylation of primary amines of unsymmetrical diamines

Verma, Sanjeev K.; Ghorpade, Ramarao; Pratap, Ajay; Kaushik, M. P.

doi:10.1039/c1gc16314k

Cited by 26 publications

(15 citation statements)

References 18 publications

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“…Transacylation using α‐aryl‐β‐keto ester 1 is sensitive to the bulkiness of amine 2 , which has the potential to facilitate regio‐ and chemoselective acylation; however, there has been no systematic study of this. With regard to the selective acylation of diamines without any protection, only a few reports are found , . For comparison, keto ester 1 , acid halides 6 , and acid anhydrides 8 underwent the reaction with N ‐methylethylenediamine 9 (Table ).…”

Section: Resultsmentioning

confidence: 99%

“…However, it is still challenging even now to acylate an amino/a hydroxy group of polyamines/amino alcohols selectively without any modification or protection of the other sites. Among selective acylation methods, monoacylation of a polyamine possessing plural equivalent amino groups is relatively easy, Recognition between primary and secondary amino groups in N ‐alkyl‐1,2‐diaminoethanes was possible by using acylimidazole, 3‐acyl‐1,3‐thiazolidine‐2‐thione, N ‐acyl‐2‐amino‐1,3‐thiazoline, N , N ‐diacyl‐2‐trifluoromethylaniline, and N ‐acyl‐ N ‐mesyl‐2‐fluorolaniline, although the control of the selectivity depended on the bulkiness of the N ‐alkyl group of diamine . These reagents were also effective for recognition of the presence of a methyl group at the α‐position .…”

Section: Introductionmentioning

confidence: 99%

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Metal‐Free O‐Selective Direct Acylation of Amino Alcohols Through Pseudo‐Intramolecular Process

et al. 2019

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Efficient α‐aryl‐β‐keto ester acylation of amine accompanied by the elimination of ethyl phenylacetate was achieved owing to the pseudo‐intramolecular process. The eliminated ethyl phenylacetate could be recycled by conversion into an α‐aryl‐β‐keto ester upon treatment with an acyl chloride in the presence of lithium bis(trimethylsilyl)amide, by which the atom economy considerably increased. Acylation using an α‐aryl‐β‐keto ester is highly sensitive to the bulkiness of the nucleophile, which facilitated the regioselective‐acylation of the less hindered amino group in diamine without protecting the other. The transacylation of α‐aryl‐β‐keto ester with N‐alkylamino alcohol resulted in chemoselective O‐acylation without protecting the amino group because the hydroxy group was attracted to the reaction site of the keto ester by forming an ammonium salt. Transacylation was demonstrated to be a practically useful tool for organic synthesis because this protocol can be conducted under mild conditions with simple manipulations in the absence of any additives such as metal catalyst and base.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Metal‐Free O‐Selective Direct Acylation of Amino Alcohols Through Pseudo‐Intramolecular Process

et al. 2019

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“…Oxidation of the benzylic carbon with KMnO 4 in the presence of NaOH and TBAB (tetrabutylammoniumbromide) afforded 4-boronobenzoic acid (4) in 50% yield over three steps. Fragments (7a~7m) and (7n~7t) were generated by condensation of various benzoic acids with piperazine or ethylenediamine [19]. 4-Boronobenzoic acid was subsequently reacted with above fragments to yield intermediates (8a~8m) and (8n~8t) [20].…”

Section: Chemistrymentioning

confidence: 99%

Expanding the structural diversity of Bcr-Abl inhibitors: Dibenzoylpiperazin incorporated with 1H-indazol-3-amine

Shan

Dong

Pan

et al. 2015

European Journal of Medicinal Chemistry

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“…, representing a commonly utilised reaction within published chemical research [13][14][15]. The reaction complements existing teachings within the undergraduate curriculum including practical synthetic techniques, S N 2 reactions, protecting group theory and analytical techniques.…”

Section: T H E R E a C T I O N C H O S E N F O R T H I S S T U D Y W mentioning

confidence: 99%

A practical experiment to teach students continuous flow and physico-chemical methods: acetylation of ethylene diamine in liquid bi-phase

et al. 2020

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Despite growing applications being reported both in academia and industry, continuous flow chemistry remains a relatively untaught field across most chemistry undergraduate courses. This is particularly true in laboratory practical classes, where it is often deemed simpler to carry out synthetic reactions in traditional batch mode using round-bottomed flasks. Herein, we report the development of an undergraduate project that utilises cheap and readily available materials to construct continuous flow reactors. The students compare the performance of different types of reactors and conditions in a biphasic selective acetylation of a symmetrical diamine. Throughout the investigation, the students can vary multiple parameters as they optimise the reaction, thus actively learning and readjusting them based on their improved understanding. The experiments give the students an appreciation of continuous flow techniques in comparison to batch.

show abstract

CDI-mediated monoacylation of symmetrical diamines and selective acylation of primary amines of unsymmetrical diamines

Cited by 26 publications

References 18 publications

Metal‐Free O‐Selective Direct Acylation of Amino Alcohols Through Pseudo‐Intramolecular Process

Metal‐Free O‐Selective Direct Acylation of Amino Alcohols Through Pseudo‐Intramolecular Process

Expanding the structural diversity of Bcr-Abl inhibitors: Dibenzoylpiperazin incorporated with 1H-indazol-3-amine

A practical experiment to teach students continuous flow and physico-chemical methods: acetylation of ethylene diamine in liquid bi-phase

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