N-<i>tert</i>-Butyldimethylsilyl Imines as Intermediates for the Synthesis of Amines and Ketones

Ortiz-Marciales, Margarita; Tirado, L. M.; Colón, Roberto; Ufret, M. L.; Figueroa, Ruth; Lebrón, Marisabel; Dejesus, M.; Martínez, Juan Carlos; Malavé, Tania

doi:10.1080/00397919808004967

Cited by 32 publications

(16 citation statements)

References 21 publications

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“…Addition of Grignard reagents to benzonitrile at low temperature, catalyzed by copper(I) bromide, and reaction with tert-butyldimethylsilyl chloride affords N-(tert-butyldimethylsilyl)imines. [69] By heating propanenitrile for 36 hours at 140 8C with 2 equivalents of triethylsilane in the presence of anhydrous zinc(II) chloride as a catalyst, a mixture of N-propyl-N-(triethylsilyl)amine (35%) and N-(2-cyanopent-3-ylidene)-N-(triethylsilyl)amine (18%) is obtained. [70] This method, however, is only of preparative significance in the case of the synthesis of N-benzylidene-N-(triethylsilyl)amine.…”

Section: Methods 5: From Nitrilesmentioning

confidence: 99%

“…[75] One of the most important applications is the synthesis of â-lactams from enolates and N-(trialkylsilyl)imines, which can be prepared in situ. [62,63,65,66,69,[76][77][78] Diastereoselective or enantioselective synthesis of highly functionalized six-membered rings have been achieved through [4 + 2]-cycloaddition reactions of N-(trimethylsilyl)imines with 2-aminobuta-1,3-dienes. [79,80] N-(Trialkylsilyl)imines also have served as starting materials for the synthesis of 2-azadienes.…”

Section: Methods 5: From Nitrilesmentioning

confidence: 99%

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Product Class 7: Imines

Padwa¹,

Bellus²

2005

Category 4. Compounds With Two Carbon Heteroatom Bonds

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Compounds with the general structure R 1 R 2 C=NR 3 , referred to as imines, were first obtained by Schiff via condensation of ketones and aldehydes with primary amines. Therefore, the condensation products are also called Schiff bases. In addition, the nominations azomethine, ketimine (derived from ketones), aldimine (derived from aldehydes), and anil (derived from anilines) are in use. It is recommended that the terms imine(s), ketimine(s), or aldimine(s) are used, rather than Schiff base(s) or azomethine(s).Since imines have to be considered as analogues of carbonyl compounds, many of the chemical properties are similar to the latter. Imines are used in new C-C bond formations, and reactions with electrophiles (e.g., aldehydes, alkyl halides), and the C=N moiety can undergo nucleophilic reactions. Generally, imines are very useful compounds in organic synthesis, as they are used in several syntheses of aza-heterocyclic compounds. Most imines are stable in an alkaline medium and therefore can be dried over potassium hydroxide. In diluted acid, however, they are easily hydrolyzed. In many cases intermediary imines cannot be isolated because of their lability. The presence of a C=N bond creates the possibility for E/Z isomerism (syn/anti). It has been recognized that such geomet-

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Section: Methods 5: From Nitrilesmentioning

confidence: 99%

Section: Methods 5: From Nitrilesmentioning

confidence: 99%

Product Class 7: Imines

Padwa¹,

Bellus²

2005

Category 4. Compounds With Two Carbon Heteroatom Bonds

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“…of aminoalcohol 8 in 24 h leading to 1a and 10a in 48 and 25% conversion, respectively, and 53% e.e. (entry 13). Using more than 1.25 equiv.…”

Section: Oxazaborolidine Reductionmentioning

confidence: 99%

“…We therefore chose to examine the borane reductions of activated ketimines via chiral oxazaborolidines which are easily obtained and allow the direct access to enantio enriched primary amines. Among these activated ketimines, we decided to study the reduction of ketone oxime O-alkylated ethers 5 (Scheme 2) which seemed to provide better results, in terms of imine access, reaction yield and/or stereoselectivity, than N-silylimines [13], 14].…”

Section: Enantiomeric Access To Ab-unsaturated Amines From Enonesmentioning

confidence: 99%

First enantioselective reductive amination of α-fluoroenones

Dutheuil

Bailly

Couve‐Bonnaire

et al. 2007

Journal of Fluorine Chemistry

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“…For example, addition of butyllithium to benzonitrile (83) followed by trapping with tert-butylchlorodimethylsilane gives the silylated imine 84, which can be reduced by borane-tetrahydrofuran to give 1-phenylpentan-1-amine (85) in a high yield (Scheme 24). [136,139] Scheme 24 One-Pot Organometal Addition and Borane Reduction To Give an a-Substituted Primary Amine [139] (72): [126] CAUTION: Borane-THF can form explosive peroxides in contact with air. It is incompatible with acids, acid chlorides, acid anhydrides, oxidizing agents, and alcohols, and reacts violently with water.…”

Section: Scheme 19 Synthesis Of A-substituted Primary Amines By Additmentioning

confidence: 99%