Hypervalent iodine-catalyzed amide and alkene coupling enabled by lithium salt activation

• Akanksha Chhikara,
• Fan Wu,
• Navdeep Kaur,
• Prabagar Baskaran,
• Alex M. Nguyen,
• Zhichang Yin,
• Anthony H. Pham and
• Wei Li

Beilstein J. Org. Chem. 2024, 20, 1405–1411, doi:10.3762/bjoc.20.122

• tethered with a nucleophile to avoid the lack of regiochemical additions (Scheme 1a) [21][22][23][24][25][26][27][28]. Intermolecular hypervalent iodine-catalyzed olefin difunctionalizations have been realized for olefin dihalogenation, dioxygenation and diamination reactions, where often the same type of

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• following example of styrene diamination by a chiral aryl iodide, the higher efficiency of the proposed catalyst compared to simpler aryl iodides was attributed to the additional stabilization of the I(III) intermediate by chelation via n–σ* interactions and hydrogen bonding [147] (Scheme 33). The

• -coupling involving aldehyde C–H bond cleavage. DABCO-derived cationic catalysts in inactivated C–H bond cleavage for alkyl radical addition to electron-deficient alkenes under photoredox catalysis conditions. Electrochemical diamination and dioxygenation of vinylarenes catalyzed by triarylamines

• -organocatalyzed vinylarene diamination. Iodoarene-organocatalyzed asymmetric CH-hydroxylation of benzylic substrates. Iodoarene-organocatalyzed asymmetric difluorination of alkenes with migration of aryl or methyl groups. Examples of 1,2-diiodo-4,5-dimethoxybenzene-catalyzed electrochemical oxidative

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

• intermolecular oxidative diamination of haloalkynes, mild reaction conditions and efficient conversion of the alkyl-substituted haloalkynes to the halogenated product were great improvements over existing methods. Stimulated by the work of Luz et al. [98] and Phan et al. [99] with Cu(BDC)MOF (BDC: 1,4

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• describe a method for alkene oxyamination and diamination that utilizes simple carbamate and urea groups as nucleophilic heteroatom donors. This method uses a tandem copper–photoredox catalyst system that is operationally convenient. The identity of the terminal oxidant is critical in these studies. Ag(I

• ) salts proved to be unique in their ability to turn over the copper cocatalyst without deleteriously impacting the reactivity of the organoradical intermediates. Keywords: copper; diamination; oxidative functionalization; oxyamination; photoredox catalysis; radical; Introduction Over the past decade, a

• combines the photoredox activation of electron-rich alkenes with copper(II)-mediated oxidation of electron-rich radicals as described by Kochi [18][19][20]. These studies resulted in the development of a general new protocol for oxyamination (Figure 1a) and diamination (Figure 1b) of alkenes. The mechanism

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

• Xiang Li,
• Pinhong Chen and
• Guosheng Liu

Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154

• ], aminofluorination [29], dioxygenation [30][31], and diamination [32][33] of alkenes could be achieved. Especially, when a nucleophile-tethered alkene is used, a cyclization product was obtained [34][35], although, stoichiometric amounts of hypervalent iodine(III) reagents were required. Due to the metal-like

• afford the diacetoxylation products in moderate yields and enantioselectivity when using Selectfluor as a terminal oxidant (Scheme 6). Diamination of alkenes The diamination of alkenes is attractive due to the significance of diamino moieties in diverse fields of the biomedicinal and pharmaceutical

• sciences. During the study of the hypervalent iodine-mediated intramolecular diamination of alkenes, Blakey and co-workers found that a catalytic version could be achieved in the presence of mCPBA to give the same product in 85% yield, which is slightly lower than the yield of the stoichiometric reaction

A survey of chiral hypervalent iodine reagents in asymmetric synthesis

• Soumen Ghosh,
• Suman Pradhan and
• Indranil Chatterjee

Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107

• al. as intermolecular diamination protocol of alkenes 56 using 9b (Scheme 12) [50]. This represented the first example of an asymmetric diamination of simple nonfunctionalized alkenes to acquire diaminated products 57. The existence of an I(III)–N bond under ligand exchange conditions and the

• diamination of alkenes. Stereoselective oxyamination of alkenes reported by Wirth et al. Enantioselective and regioselective aminofluorination by Nevado et al. Fluorinated difunctionalization reported by Jacobsen et al. Aryl rearrangement reported by Wirth et al. α-Arylation of β-ketoesters. Asymmetric α

Hypervalent iodine-mediated Ritter-type amidation of terminal alkenes: The synthesis of isoxazoline and pyrazoline cores

• Sang Won Park,
• Soong-Hyun Kim,
• Jaeyoung Song,
• Ga Young Park,
• Darong Kim,
• Tae-Gyu Nam and
• Ki Bum Hong

Beilstein J. Org. Chem. 2018, 14, 1028–1033, doi:10.3762/bjoc.14.89

• [23][24][25][26][27]. Results and Discussion As depicted in Scheme 1, we have previously reported an inter-/intramolecular alkene diamination using either N-iodosuccinimide (NIS) or a phenyliodine diacetate (PIDA)/halide additive combination [28][29][30]. Vinylanilines and vinylaminopyridines in

Enantioselective dioxytosylation of styrenes using lactate-based chiral hypervalent iodine(III)

• Morifumi Fujita,
• Koki Miura and
• Takashi Sugimura

Beilstein J. Org. Chem. 2018, 14, 659–663, doi:10.3762/bjoc.14.53

• diacetoxylation [38][39][50] and diamination [30][49] of styrene. In summary, the reaction of styrenes with lactate-derived aryl-λ3-iodanes gave the dioxytosylated product with an ee of 70–96%. Series of lactate-based hypervalent iodine reagents. Enantioselective dioxytosylation of styrene as a seminal example

Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

• Brett N. Hemric and
• Qiu Wang

Beilstein J. Org. Chem. 2016, 12, 22–28, doi:10.3762/bjoc.12.4

• transformation, integrating an electrophilic amination with a nucleophilic oxygenation, builds upon our recent development in copper-catalyzed olefin difunctionalization, such as copper-catalyzed diamination [40] and amino lactonization [34]. This strategy overcomes common issues of chemo- and regioselectivity

Copper-catalyzed aminooxygenation of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives

• Yan Li,
• Xue Zhou,
• Guangfan Zheng and
• Qian Zhang

Beilstein J. Org. Chem. 2015, 11, 2721–2726, doi:10.3762/bjoc.11.293

• modes of NFSI [37][38][39][40][41], especially as a nitrogen-centred radical. In this context, we have realized copper-catalyzed benzylic sp3 C–H amination [42], aminative multiple functionalization of alkynes [43], diamination, aminocyanation [44] and aminofluorination of alkenes [45], as well as

Synthesis and chemosensing properties of cinnoline-containing poly(arylene ethynylene)s

• Natalia A. Danilkina,
• Petr S. Vlasov,
• Semen M. Vodianik,
• Andrey A. Kruchinin,
• Yuri G. Vlasov and
• Irina A. Balova

Beilstein J. Org. Chem. 2015, 11, 373–384, doi:10.3762/bjoc.11.43

• depicted in Figure 9 and Figure 11 were observed. Previously palladium(II)-alkyne π-complexes have been proposed as intermediates in Pd(II)-catalyzed diamination of alkynes [63], enyne coupling [64], hydroarylation of alkynes [65], inramolecular carbocyclization [66] and other reactions. Some types of

One-pot stereoselective synthesis of α,β-differentiated diamino esters via the sequence of aminochlorination, aziridination and intermolecular S_N2 reaction

• Yiwen Xiong,
• Ping Qian,
• Chenhui Cao,
• Haibo Mei,
• Jianlin Han,
• Guigen Li and
• Yi Pan

Beilstein J. Org. Chem. 2014, 10, 1802–1807, doi:10.3762/bjoc.10.189

• substrates and proceed with excellent stereo- and regioselectivity (anti:syn >99:1) . Keywords: aminohalogenation; diamination; α,β-diamino ester; one-pot; stereoselectivity; Introduction α,β-Diamino acid derivatives are one of the most important classes of nitrogen-containing bioactive compounds [1][2

• access for the generation of α,β-diamino esters, which usually employ palladium or osmium as catalysts [23][24][25]. The electrophilic diamination reaction is an alternative methodology [26][27][28], which makes use of α,β-unsaturated esters as starting materials to form imidazoline diamine derivatives

New developments in gold-catalyzed manipulation of inactivated alkenes

• Michel Chiarucci and
• Marco Bandini

Beilstein J. Org. Chem. 2013, 9, 2586–2614, doi:10.3762/bjoc.9.294

• process. In 2009 Muñiz and coworkers reported on the diamination of alkenes catalyzed by Ph3PAuOAc in presence of PhI(OAc)2 (Scheme 31) [74]. The process led to the formation of two new C–N bonds under mild conditions with excellent yields. A mechanistic rationale was also provided dealing with initial

• . Enantioselective intramolecular hydroalkylation of allylic alcohols with aldehydes catalyzed by 20c and chiral secondary amine. Gold-catalyzed intramolecular diamination of alkenes. Gold-catalyzed aminooxygenation and aminoarylation of alkenes. Gold-catalyzed carboamination, carboalkoxylation and

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

• 139 were obtained via gold(I)-catalyzed intramolecular dihydroamination of allenes with N,N′-disubstituted ureas 138. Iglesias et al. reported a complimentary diamination of alkenes 140 with homogeneous gold catalysts [66]. The key step is an intramolecular alkyl–nitrogen bond formation from a gold