Palladium-catalyzed synthesis of N-arylated carbazoles using anilines and cyclic diaryliodonium salts

• Stefan Riedmüller and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2013, 9, 1202–1209, doi:10.3762/bjoc.9.136

• present an alternative Pd-catalyzed method for the construction of N-substituted carbazoles based on a stable, cyclic iodonium salt and electron-deficient anilines [24][25]. In the initial C–N bond-forming step of this cascade reaction, a ring opening of the cyclic iodonium salt through the amine is

Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

• Josué M. Silla,
• Rodrigo A. Cormanich,
• Roberto Rittner and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2013, 9, 1127–1134, doi:10.3762/bjoc.9.125

• electron donors than halogens in these cases. This interaction is explicitly expressed for 8b and 9c by means of X∙∙∙B bond paths in QTAIM (Figure 7). Indeed, the B–C–C(N) bond angle in 8c and 9c is significantly curved to allow the formation of a four-membered ring, reflecting the effectiveness of the X/B

Efficient synthesis of β’-amino-α,β-unsaturated ketones

• Isabelle Abrunhosa-Thomas,
• Aurélie Plas,
• Nishanth Kandepedu,
• Pierre Chalard and
• Yves Troin

Beilstein J. Org. Chem. 2013, 9, 486–495, doi:10.3762/bjoc.9.52

• reaction of chiral imines with enolates derived from Weinreb amides [13][14]. In previous work on the asymmetric synthesis of 2,6-disubstituted piperidines by C–N bond formation, we demonstrated that intramolecular aza-Michael ”type” cyclisation [15] using a β'-carbamate-α,β-unsaturated ketone

Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

• Rajendra Surasani,
• Dipak Kalita,
• A. V. Dhanunjaya Rao and
• K. B. Chandrasekhar

Beilstein J. Org. Chem. 2012, 8, 2004–2018, doi:10.3762/bjoc.8.227

• report on coupling of amides, amino acid esters and phenols with N-protected 4-bromo-7-azaindole derivatives. Keywords: 7-azaindole; C–N bond; C–O bond; ligand; palladium catalyst; Introduction Palladium-catalyzed C–N and C–O bond-forming reactions between 4-substituted 7-azaindoles and amides, amines

• prepare [6]. Initially, coupling of 4-bromo-1-ethyl-1H-pyrrolo[2,3-b]pyridine (1d) with phenylmethanamine (4a) was selected as a model reaction to optimize the reaction condition of C–N-bond formation of amines. The experimental results are summarized in Table 3. After the screening of various ligands

• amines. As seen from Table 4, the cross-coupling reaction of N-protected 4-bromo-7-azaindoles 1a–1d with various amines 4a–4f proved to be general under the optimized conditions to get the coupled products 5a–5f in very good yield (88–94%) within a reasonable time of 2.5 to 3 h. The C–N-bond-forming

Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

• Vadim A. Soloshonok,
• José Luis Aceña,
• Hisanori Ueki and
• Jianlin Han

Beilstein J. Org. Chem. 2012, 8, 1920–1928, doi:10.3762/bjoc.8.223

• -derived enolates [65][66][67][68][69][70], in particular, under similar conditions. Thus, the ionized form of α-hydroxy intermediate 17 can undergo the cleavage of the glycine C–N bond [65][68][69][70] resulting in the formation of neutral complex 18. Previously, we demonstrated that in situ formed

N-Heterocyclic carbene–palladium(II)-1-methylimidazole complex catalyzed Mizoroki–Heck reaction of aryl chlorides with styrenes

• Ting-Ting Gao,
• Ai-Ping Jin and
• Li-Xiong Shao

Beilstein J. Org. Chem. 2012, 8, 1916–1919, doi:10.3762/bjoc.8.222

• -diisopropylphenyl)imidazolium chloride], and 1-methylimidazole in a one-step procedure in high yield, was an effective catalyst in C–C and C–N bond-formation reactions [37][38][39][40][41][42][43][44]. In our continuing investigations on the further applications of this complex in organic synthesis, we found that

Palladium-catalyzed dual C–H or N–H functionalization of unfunctionalized indole derivatives with alkenes and arenes

• Gianluigi Broggini,
• Egle M. Beccalli,
• Andrea Fasana and
• Silvia Gazzola

Beilstein J. Org. Chem. 2012, 8, 1730–1746, doi:10.3762/bjoc.8.198

• regenerates the Pd(0) species. The intramolecular Pd(II)-catalyzed reaction of the 1-allyl-2-indolecarboxamides 41 leads to the pyrazino[1,2-a]indoles 43 through the conversion of the olefinic C–H bond into a C–N bond (Scheme 21) [79]. The cyclization process resulted in the initially formed exomethylenic

Synthesis of conformationally restricted glutamate and glutamine derivatives from carbonylation of orthopalladated phenylglycine derivatives

• Esteban P. Urriolabeitia,
• Eduardo Laga and
• Carlos Cativiela

Beilstein J. Org. Chem. 2012, 8, 1569–1575, doi:10.3762/bjoc.8.179

• different reactivity. Therefore, the attack of the oxygen of an O-bonded alcohol on the electrophilic acyl carbon in our complexes seems to be favoured, since no demethylation is involved, and the C–O coupling occurs selectively instead of the intramolecular C–N bond formation. It seems that the reaction is

N-Heterocyclic carbene-catalyzed direct cross-aza-benzoin reaction: Efficient synthesis of α-amino-β-keto esters

• Takuya Uno,
• Yusuke Kobayashi and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2012, 8, 1499–1504, doi:10.3762/bjoc.8.169

• migration of the N-acyl glycine derivatives [18]. The other consists of C–N bond-forming reactions, such as (c) a rhodium-catalyzed N–H insertion reaction with α-diazo-β-keto esters [19][20][21], and (d) α-oxidation of β-keto esters to the corresponding oximes and the subsequent hydrogenation [22]. However

Cation affinity numbers of Lewis bases

• Christoph Lindner,
• Raman Tandon,
• Boris Maryasin,
• Evgeny Larionov and
• Hendrik Zipse

Beilstein J. Org. Chem. 2012, 8, 1406–1442, doi:10.3762/bjoc.8.163

• cation adduct than in the neutral amine. Figure 2 shows the projection through the C–N bond of one of the isopropyl-groups in 16Me. Trialkyl- and triarylphosphanes are equally potent nucleophiles, whose use in catalytic processes is, however, often limited due to their oxygen sensitivity. Table 2 lists

• calculated for these systems thus represent the reaction enthalpies for the formation of ion-dipole complexes. Aside from DABCO this is the case for 345, 45, and 347. The C–N bond distances of the energetically best conformations of these complexes range from 2.8 Å to 4.0 Å. As a reference bond length the C

• –N distance in pyridine-trityl adduct (1TT), which amounts to 1.57 Å, can be used. A slightly increased C–N bond length can be found for the TCA-adduct of quinuclidine 53 (1.76 Å), which is in distinct contrast to the structurally similar DABCO. It should be added that all other electrophiles

Approaches to α-amino acids via rearrangement to electron-deficient nitrogen: Beckmann and Hofmann rearrangements of appropriate carboxyl-protected substrates

• Sosale Chandrasekhar and
• V. Mohana Rao

Beilstein J. Org. Chem. 2012, 8, 1393–1399, doi:10.3762/bjoc.8.161

• . The geometry around the partial double bond of the amide C–N linkage in 5a is also Z (Figure 1). This is probably a consequence of steric repulsion between the N-substituent and the phenyl residue in the alternative E isomer. NMR spectra likewise did not indicate isomerism around the amide C–N bond in

An intramolecular inverse electron demand Diels–Alder approach to annulated α-carbolines

• Zhiyuan Ma,
• Feng Ni,
• Grace H. C. Woo,
• Sie-Mun Lo,
• Philip M. Roveto,
• Scott E. Schaus and
• John K. Snyder

Beilstein J. Org. Chem. 2012, 8, 829–840, doi:10.3762/bjoc.8.93

• 3-arylpyridines also found application [43][44], and likewise falls into the category of indole ring closure onto an existing substituted pyridine, though in this case with the formation of the C–N bond. More recently, the group of Cuny has reported two strategies that exploit cross-couplings to

• –Buchwald cross-coupling onto a 2-bromoindole, with formation of the pyridine was reported by Dodd [59], and C–N bond closures in presumed nitrogen-radical processes have also been reported by Narasaka [60][61]. Electrocyclic ring closures forming the pyridine ring from 2-aminoindole-derived intermediates

Synthesis of axially chiral oxazoline–carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe₂

• Feijun Wang,
• Shengke Li,
• Mingliang Qu,
• Mei-Xin Zhao,
• Lian-Jun Liu and
• Min Shi

Beilstein J. Org. Chem. 2012, 8, 726–731, doi:10.3762/bjoc.8.81

• , affording the corresponding Au(I) complexes in moderate to high yields. Keywords: axially chiral ligand; gold; N-heterocyclic carbenes; N-naphthyl framework; Introduction During the past decade, with an explosive growth of asymmetric homogeneous gold catalysis in C–C, C–O, or C–N bond formations, the

Carbohydrate-auxiliary assisted preparation of enantiopure 1,2-oxazine derivatives and aminopolyols

• Marcin Jasiński,
• Dieter Lentz and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2012, 8, 662–674, doi:10.3762/bjoc.8.74

• low yield. The formation of 20 could be explained by a subsequent SmI2-mediated reduction of the C=N bond formed by ring opening of 19, which contains a hemiaminal moiety. This suggestion is supported by the 1H NMR spectrum of 19 in which a second set of signals could be easily detected. Thus, the

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• precursor 49 in situ through a Pd/Cu mediated coupling reaction between (trimethylsilyl)acetylene (TMSA) with an aryl iodide, followed by a desilylation reaction. The subsequent addition of the third partner, an o-iodoanilide derivative, allowed a Pd/Cu tandem C–C/C–N-bond-forming reaction. The main

Reductive amination with zinc powder in aqueous media

• Giovanni B. Giovenzana,
• Daniela Imperio,
• Andrea Penoni and
• Giovanni Palmisano

Beilstein J. Org. Chem. 2011, 7, 1095–1099, doi:10.3762/bjoc.7.125

• dehydrative condensation to give an imine or an iminium ion, the latter being formally hydrogenated to the final amine product. The selectivity of the reducing agent is crucial as it should efficiently reduce the C=N bond of the intermediate while leaving unaffected the potentially reducible carbonyl compound

• . In addition, the desired reduction of the C=N bond may be accelerated by working in the presence of weak acids, thus allowing protonation of the C=N nitrogen atom but not of the carbonyl oxygen; the reducing agent, usually a hydride, should then be reasonably stable in the presence of acidic

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• enriched secondary propargyl alcohols led to the chiral oxetan-3-one with no apparent racemization (Scheme 20). 3 Gold-catalyzed C–N bond formations Many organic compounds containing nitrogen exhibit important biological and pharmaceutical properties. As with gold-catalyzed C–O bond formation, the directly

• . In addition to intermolecular addition, Mukherjee and Widenhoefer recently reported a gold(I)-catalyzed intramolecular amination of allylic alcohols 130 with alkylamines (Scheme 23) [61]. 3.2 Imines as nucleophiles Gold-catalyzed cyclizations of O-propioloyl oximes via C–N bond formation followed by

• the Brønsted acid is both a chiral catalyst for the asymmetric cycloaddition and assists to facilitate the gold complex catalyzed hydroamination. Muratore et al. have reported an interesting example of C–N bond formation for the construction of chiral nitrogen-containing fused heterocycles 400 [191

Isotopic labelling studies for a gold-catalysed skeletal rearrangement of alkynyl aziridines

• Paul W. Davies,
• Nicolas Martin and
• Neil Spencer

Beilstein J. Org. Chem. 2011, 7, 839–846, doi:10.3762/bjoc.7.96

• requires fission of three bonds: The propargylic C–N bond in ring expansion; the aryl–aziridinyl C–C bond in the 1,2 shift and the propargylic C–H bond for aromatisation (Scheme 3). The positioning of a deuterium atom at the benzylic carbon in 4 enables the carbons of the aziridine ring to be distinguished

Single enantiomer synthesis of α-(trifluoromethyl)-β-lactam

• Václav Jurčík,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2011, 7, 759–766, doi:10.3762/bjoc.7.86

• explored for the hydrogenolysis of 5a, however cleavage of the C–N bond proved very difficult and a satisfactory method could not be found. Therefore, (S)-α-(p-methoxyphenyl)ethylamine (3b) was explored as an alternative amine for the aza-Michael reaction, as removal of this amine using ceric ammonium

C–C (alkynylation) vs C–O (ether) bond formation under Pd/C–Cu catalysis: synthesis and pharmacological evaluation of 4-alkynylthieno[2,3-d]pyrimidines

• Dhilli Rao Gorja,
• K. Shiva Kumar,
• K. Mukkanti and
• Manojit Pal

Beilstein J. Org. Chem. 2011, 7, 338–345, doi:10.3762/bjoc.7.44

• case of MeOH. While triethylamine was used as a base in all these cases, the use of a secondary amine, e.g., pyrrolidine was also examined. A side product was observed in this case due to the C–N bond forming reaction between 1a and pyrrolidine and was identified as 4-(N-pyrrolidinyl)-5,6,7,8

Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

• Carolin Fischer and
• Burkhard Koenig

Beilstein J. Org. Chem. 2011, 7, 59–74, doi:10.3762/bjoc.7.10

• specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis. Keywords: biologically active compounds; boronic acid; copper; N-arylation; palladium; Introduction Palladium- and

α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

• David. M. Hodgson and
• Zhaoqing Xu

Beilstein J. Org. Chem. 2010, 6, 978–983, doi:10.3762/bjoc.6.110

• group undergo cleavage at the formally benzylic C–N bond, leading to α-aminophosphonates. With β-alkyl groups, regioselectivity is influenced by the presence or absence of an N-substituent. N-Ts Cis-β-alkyl-substituted aziridinylphosphonates give β-aminophosphonates [32], whereas both N-Boc cis- and

Molecular recognition of organic ammonium ions in solution using synthetic receptors

• Andreas Späth and
• Burkhard König

Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32

Structural studies on encapsulation of tetrahedral and octahedral anions by a protonated octaaminocryptand cage

• I. Ravikumar,
• P. S. Lakshminarayanan,
• E. Suresh and
• Pradyut Ghosh

Beilstein J. Org. Chem. 2009, 5, No. 41, doi:10.3762/bjoc.5.41

• , N3, N5, N6, N7 and N8, from all three strands of the cryptand moiety are protonated, which is evident by the comparatively longer C–N bond distances of these nitrogen atoms with the neighboring carbons (Table 1). The encapsulated perchlorate is involved in two N–H···O and five O–H···O hydrogen

Variations in product in reactions of naphthoquinone with primary amines

• Marjit W. Singh,
• Anirban Karmakar,
• Nilotpal Barooah and
• Jubaraj B. Baruah

Beilstein J. Org. Chem. 2007, 3, No. 10, doi:10.1186/1860-5397-3-10

• -naphthoquinone with 4-aminothiophenol and 1,4-naphthoquinone with 4-aminophenol are compared. The former leads to C-S and the latter to C-N bond formation. The reaction of 1,4-naphthoquinone with 4-aminothiophenol in an NMR tube is studied to explain that 2-(4-anilinothiolato) 1,4-naphthoquinone derivative to be

•  3c). Surprisingly in this reaction the product formed is through C-S bond formation rather than C N-bond formation (Scheme 4). The presence of a few well-separated peaks of the products from the starting materials in the NMR spectra (designated by A) shows the formation of the one product with time

• complete understanding of the mechanism but the observations hint towards a radical mechanism rather than an ionic mechanism. In contrast to the reaction of 4-aminothiophenol with 1,4-naphthoquinone the reaction of 4-aminophenol gave the expected product through C-N bond formation. The structures of the