Synthesis Of Vicinal Diamines Research Articles

Synthesis of 2,3‐Diaminoindolesvia a Copper‐Iodine Co‐catalytic Strategy

Comprehensive SummaryA one‐pot synthesis of vicinal diamines using indoles, azoles and phenothiazines in a tandem multi‐component reaction is developed. The utilization of a copper‐iodine co‐catalytic system enables the generation of a diverse range of vicinal diaminoindoles with good selectivity and moderate to good yields. An attractive aspect of this method is that it can be conducted under mild and environmentally friendly conditions, showcasing its potential as an alternative approach for synthesizing vicinal diamines. Moreover, the use of a multicomponent tandem reaction highlights the power and versatility of such strategies in synthetic chemistry.

One‐Pot Three‐Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination

AbstractA synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron‐poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium‐catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl, and hetereoaryl groups with complete regioselectivity and high diastereoselectivity. The reaction exhibits a high functional‐group tolerance. Importantly, either nitrogen atom of the imidazolidine products can be selectively deprotected, while removal of the aminal tether can be achieved in a single step under mild conditions to reveal the free diamine. We expect that this work will promote the further use of mixed aminal tethers in organic synthesis.

One‐Pot Three‐Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination

A synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron-poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium-catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl, and hetereoaryl groups with complete regioselectivity and high diastereoselectivity. The reaction exhibits a high functional-group tolerance. Importantly, either nitrogen atom of the imidazolidine products can be selectively deprotected, while removal of the aminal tether can be achieved in a single step under mild conditions to reveal the free diamine. We expect that this work will promote the further use of mixed aminal tethers in organic synthesis.

ChemInform Abstract: A Novel One‐Pot Synthesis of Vicinal Diamines with Benzaldehyde and Aniline Derivatives Mediated by BiCl3/Zn.

AbstractThe novel method allows the condensation of benzaldehydes and anilines to imines and reductive coupling of imines in a one‐pot manner to give vicinal diamines as diastereomeric mixture.

ChemInform Abstract: A Catalytic Tethering Strategy: Simple Aldehydes Catalyze Intermolecular Alkene Hydroaminations.

Herein we describe a catalytic tethering strategy in which simple aldehyde precatalysts enable, through temporary intramolecularity, room-temperature intermolecular hydroamination reactivity and the synthesis of vicinal diamines. The catalyst allows the formation of a mixed aminal from an allylic amine and a hydroxylamine, resulting in a facile intramolecular hydroamination event. The promising enantioselectivities obtained with a chiral aldehyde also highlight the potential of this catalytic tethering approach in asymmetric catalysis and demonstrate that efficient enantioinduction relying only on temporary intramolecularity is possible.

A Catalytic Tethering Strategy: Simple Aldehydes Catalyze Intermolecular Alkene Hydroaminations

Herein we describe a catalytic tethering strategy in which simple aldehyde precatalysts enable, through temporary intramolecularity, room-temperature intermolecular hydroamination reactivity and the synthesis of vicinal diamines. The catalyst allows the formation of a mixed aminal from an allylic amine and a hydroxylamine, resulting in a facile intramolecular hydroamination event. The promising enantioselectivities obtained with a chiral aldehyde also highlight the potential of this catalytic tethering approach in asymmetric catalysis and demonstrate that efficient enantioinduction relying only on temporary intramolecularity is possible.

Homocoupling of aldimines mediated by zirconocene: synthesis of vicinal diamines and imidazolidines

The reductive coupling of imines in the presence of the lanthanide-originated zirconocene equivalent allows the synthesis of vicinal diamines or imidazolidines under mild conditions in good yields with high diastereoselectivity.

Synthesis of vicinal diamines via Zn–H 2O–CO 2-induced reduction of aromatic imines in supercritical carbon dioxide

Zn–H 2O–CO 2 is a good reducing reagent for the reduction of imines in supercritical carbon dioxide (scCO 2). They provide the corresponding vicinal diamines in moderate to good yields. The results showed that carbon dioxide plays an important role as both solvent and reagent.

Samarium/NBS System Mediated Dimerisation of Imines: A Convenient Route to Vicinal Diamines

A convenient, efficient and stereoselective synthesis of vicinal diamines in satisfactory yields by dimerisation of imines mediated by a Sm/NBS system has been performed.

Practical Asymmetric Synthesis of Vicinal Diamines through the Catalytic Highly Enantioselective Alkylation of Glycine Amide Derivatives

Practical Asymmetric Synthesis of Vicinal Diamines through the Catalytic Highly Enantioselective Alkylation of Glycine Amide Derivatives

ChemInform Abstract: A New Version of the Reverse‐Cope Elimination Initiated by the Nucleophilic Addition of Allylamines to Nitrones: A Synthesis of Vicinal Diamines.

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A new version of the reverse-Cope elimination initiated by the nucleophilic addition of allylamines to nitrones: a synthesis of vicinal diamines

Attempts to utilize the sugar-derived nitrones 1 in enantioselective [1,3]dipolar cycloadditions with protected allylamines 6 are only partly successful, giving mixtures of the expected adducts 7. However, reactions between nitrones 1 and unprotected allylamine 11 follow a different pathway involving sequential nucleophilic addition to the nitrone by the amine, reverse-Cope cyclization and Meisenheimer rearrangement leading to the 1,2,5-oxadiazinanes 12 and 13. Similar reactions with the benzaldehyde derived nitrone 8 are successful, giving the trans-oxadiazinanes 24, 33 and the stereoisomers 38 and 39 from linalylamine 37, but only when the terminus of the allylamine is unsubstituted are the reactions efficient. A range of N-alkylallylamines 43, 45, 47 and 49, however, react smoothly with nitrone 8, as competing imine formation is precluded. Various mechanistic aspects are discussed, along with the effects of aryl substituents in N-benzylallylamines 57 and at the 4-position (59) of the nitrone 8, none of which is found to enhance the overall reaction rate. The initial oxadiazinanes are useful as precursors to both aminohydroxylamines 69 and vicinal diamine derivatives 70.

Organic reaction in water. Part 4. New synthesis of vicinal diamines using zinc powder-promoted carbon–carbon bond formation

Reductive coupling of aromatic imines is performed by the use of zinc powder and additives such as NH4Cl and L-tyrosine in water without any organic solvents under mild conditions to give the corresponding vicinal diamines in good yields; cross-coupling of N-benzylideneaniline and benzaldehyde similarly proceeds in aqueous media to afford the corresponding 2-aminoalcohol.

Synthesis of vicinal diamines from cyclic sulfates

Necleopila opining of cyclic sulfates with secondary amaturs followed by treatment with base leads to elimination of sulfate and formation of an aziridinium ion This can in turn be opened by a second equivalent of the amine to yield a vicinal dianune or by a second nucleophile to give an α- functionalized amine

Synthesis of vicinal diamines by SmI 2-promoted reduction of N-(N′,N′-Dialkylaminoalkyl)benzotriazoles

N-(N′,N′-Dialkylaminoalkyl)benzotriazoles, derived from aldehydes and secondary amines, react with one equivalent of samarium iodide (SmI 2), under mild conditions to afford tertiary vicinal diamines, as a result of C-C coupling between two dialkylaminoalkyl moieties.