Catalyst free C–N bond formation by the reaction of amines with diimides: bulky guanidines

Baishya, Ashim; Peddarao, Thota; Barman, Milan Kumar; Nembenna, Sharanappa

doi:10.1039/c5nj01612f

Cited by 18 publications

(10 citation statements)

References 57 publications

(44 reference statements)

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“…The precursors were prepared by following literature procedures. 24,25 Anhydrous solvents toluene and n-hexane were collected from mBRAUN solvent purification system and used as such. Deuterated benzene (C 6 D 6 ) was dried over a sodium mirror in vacuum prior to use.…”

Section: General Proceduresmentioning

confidence: 99%

“…, were prepared by previously reported literature procedures by using piperazine (or dilithiated piperazine) and N,N'-diaryl carbodiimide as precursors (Scheme 1). 24,25 N,N -diaryl carbodiimides are important starting materials for the synthesis of several nitrogen-donor ligands such as amidines, formamidines, mono-or biguanidines, N-heterocyclic carbene-carbodiimide (NHC-CDI) adducts, etc. We have previously reported several bulky nitrogen-donor ligands such as 1,3-disubstituted formamidines, tetra-substituted guanidines, bis-guanidines, NHC-CDI adducts by using N,N -diaryl CDIs as precursors.…”

Section: Synthesis and Spectroscopic Characterizationmentioning

confidence: 99%

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Bimetallic aluminum alkyl and iodide complexes stabilized by a bulky bis-guanidinate ligand

et al. 2018

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A series of bulky bis-guanidine ligands such as L 1 (2H), L 2 (2H) and L 3 (2H), where L = {ArNCNAr} 2 {μ-N(C 2 H 4) 2 N}, for L 1 (2H) (Ar = 2, 6-Me 2-C 6 H 3), L 2 (2H) (Ar = 2, 4, 6-Me 3-C 6 H 2) and (L 3 (2H)) (Ar = 2, 6-i Pr 2-C 6 H 3) have been utilized to synthesize four-membered dinuclear aluminum heterocycles. Deprotonation of L 1−3 (2H) (1.0 equiv.) upon treatment with trimethyl aluminum (2.1 equiv.) in toluene led to the formation of bimetallic aluminum alkyls: [L 1 (AlMe 2) 2 ] (1), [L 2 (AlMe 2) 2 ] (2) and [L 3 (AlMe 2) 2 ] (3). Aluminum halide complex i.e., [L 3 (AlI 2) 2 ](4) was obtained by the reaction of compound 3 with four equivalents of molecular iodine in toluene at 80 • C, in which alkyl-halide exchange occurred. All the compounds (1-4) were confirmed by multinuclear (1 H and 13 C) magnetic resonance spectroscopy. Furthermore, compounds 2-4 were confirmed by single crystal X-ray structural analysis. All the compounds 1-4 display the expected number of signals in the 1 H and 13 C NMR spectra and are consistent with their compositions. The solid state structures of 1-4 reveal that each aluminum center is bonded to the monoanionic guanidinate ligand in N ,N-chelated fashion and the other two sites are occupied by alkyl or halide ligands, resulting in a distorted tetrahedral geometry.

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Section: General Proceduresmentioning

confidence: 99%

Section: Synthesis and Spectroscopic Characterizationmentioning

confidence: 99%

Bimetallic aluminum alkyl and iodide complexes stabilized by a bulky bis-guanidinate ligand

et al. 2018

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“…Bulky N, N ’ ‐diaryl carbodiimides are important precursors for the preparation of bulky amidines, guanidines etc . Alkyl carbodiimides such as dicyclohexyl carbodiimide (DCC), diisopropyl carbodiimide (DIC) and di‐tert‐butylcarbodiimide (DTC) are commercially available.…”

Section: Resultsmentioning

confidence: 99%

Air Stable N‐Heterocyclic Carbene‐Carbodiimide (“NHC‐CDI”) Adducts: Zwitterionic Type Bulky Amidinates

et al. 2016

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Herein we report a library of N-heterocyclic carbene-carbodiimide ("NHC-CDI") adducts i. e., zwitterionic type amidinates from the reaction between N,N' -diaryl substituted symmetrical or unsymmetrical carbodiimide and N-heterocyclic carbene at room temperature conditions. Generally, normal amidinates are air and moisture sensitive; that can be achieved by the treat-ment of amidines with base under air and moisture free conditions. In contrast, these new zwitterionic type bulky amidinate compounds are neutral and air stable. All new 31 examples of "NHC-CDI" adducts were characterized by 1 H, 13 C{ 1 H} and HRMS analyses. Further, six compounds were confirmed by single crystal X-ray structural analysis.

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“…[35][36][37] Many therapeutic agents have been constructed from this scaffold such as Cimetidine 1 (treatment of heartburn and peptic ulcers) and Pinacidil 2 (treatment of hypertension) (Scheme 1). Typical synthesis of guanidinei nvolves reactionb etween an amine and guanylating agents such as isothioureas, [38][39][40] carbodiimide, [41][42][43][44] amidine, [45] cyanamide, [46][47][48][49] pyrrazole, [50] triflylguanidines [51] and thiourea. [52][53][54] Among them, thiourea are the most promising guanylating agentb ecause of their stabilitya nd ease of preparation.…”

Section: Introductionmentioning

confidence: 99%

Micelle‐Enabled One‐Pot Guanidine Synthesis in Water Directly from Isothiocyanate using Hypervalent Iodine(III) Reagents under Mild Conditions

Srisa

Tankam

Sukwattanasinitt

et al. 2019

Chemistry An Asian Journal

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In this work, we developed a one‐pot synthesis of guanidine directly from isothiocyanate using DIB (diacetoxyiodobenzene) as a desulfurizing agent under micellar conditions in water. Our optimization study revealed that the use of 1 % TPGS‐750‐M as a surfactant with NaOH as an additive base at room temperature can convert a variety of isothiocyanates and amines into corresponding guanidines in excellent yields (69–95 %). This synthetic process in water can be applied to prepare guanidine at gram‐scale quantity. Our aqueous micellar medium also demonstrated high reusability as the reaction can be performed for several cycles without losing its efficiency. The reaction is metal‐free, utilizes water as solvent and practical (room temperature and open flask).

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Catalyst free C–N bond formation by the reaction of amines with diimides: bulky guanidines

Cited by 18 publications

References 57 publications

Bimetallic aluminum alkyl and iodide complexes stabilized by a bulky bis-guanidinate ligand

Bimetallic aluminum alkyl and iodide complexes stabilized by a bulky bis-guanidinate ligand

Air Stable N‐Heterocyclic Carbene‐Carbodiimide (“NHC‐CDI”) Adducts: Zwitterionic Type Bulky Amidinates

Micelle‐Enabled One‐Pot Guanidine Synthesis in Water Directly from Isothiocyanate using Hypervalent Iodine(III) Reagents under Mild Conditions

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