132910-76-0Relevant academic research and scientific papers
Conversion of medium-sized lactams to α-vinyl or α-acetylenyl azacycles via N,O-acetal TMS ethers
Kim, Minjun,Jang, Jaebong,Choi, Goyoung,Chung, Sungkyun,Lim, Changjin,Hur, Joonseong,Kim, Hyun Su,Na, Younghwa,Son, Woo Sung,Suh, Young-Ger,Jung, Jong-Wha,Kim, Seok-Ho
, (2018)
α-Vinyl or α-acetylenyl azacycles were easily synthesized from 7- to 9-membered lactams and 6- to 9-membered lactams via N,O-acetal trimethylsilyl (TMS) ethers. Organocopper and organostannane reagents afforded reasonable yields for the respective N-acyliminium ion vinylation and acetylenylation intermediates generated from N,O-acetal TMS ethers in the presence of a Lewis acid.
A One-Pot Iodo-Cyclization/Transition Metal-Catalyzed Cross-Coupling Sequence: Synthesis of Substituted Oxazolidin-2-ones from N-Boc-allylamines
Chaumont-Olive, Pauline,Cossy, Janine
supporting information, (2020/05/14)
A one-pot iodo-cyclization/transition metal-catalyzed cross-coupling sequence is reported to access various C5-functionalized oxazolidin-2-ones from unsaturated N-Boc-allylamines. Depending on the Grignard reagents used for the cross-coupling, e.g., aryl- or cyclopropylmagnesium bromide, a cobalt or copper catalyst has to be used to obtain the functionalized oxazolidin-2-ones in good yields.
Rhodium-Catalyzed Asymmetric Intramolecular Hydroamination of Allenes
Berthold, Dino,Geissler, Arne G. A.,Giofré, Sabrina,Breit, Bernhard
supporting information, p. 9994 - 9997 (2019/07/04)
The rhodium-catalyzed asymmetric intramolecular hydroamination of sulfonyl amides with terminal allenes is reported. It provides selective access to 5- and 6-membered N-heterocycles, scaffolds found in a large range of different bioactive compounds. Moreover, gram scale reactions, as well as the application of suitable product transformations to natural products and key intermediates thereof are demonstrated.
Enantioselective Aza-Heck Cyclizations of N-(Tosyloxy)carbamates: Synthesis of Pyrrolidines and Piperidines
Ma, Xiaofeng,Hazelden, Ian R.,Langer, Thomas,Munday, Rachel H.,Bower, John F.
, p. 3356 - 3360 (2019/03/07)
Pd(0)-systems modified with SPINOL-derived phosphoramidate ligands promote highly enantioselective aza-Heck cyclizations of alkenyl N-(tosyloxy)carbamates. The method provides versatile access to challenging N-heterocycles and represents the broadest scope enantioselective aza-Heck protocol developed to date.
ARYL-SULFONAMIDE AND ARYL-SULFONE DERIVATIVES AS TRPML MODULATORS
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Page/Page column 61, (2018/12/03)
The new arylsulfonamide and arylsulfone derivatives are modulators of TRPML and are useful in treating disorders related to TRPML activities and lysosome functions such as acid-related disorders and cancer.
Catalytic Synthesis of N-Heterocycles via Direct C(sp3)-H Amination Using an Air-Stable Iron(III) Species with a Redox-Active Ligand
Bagh, Bidraha,Broere, Dani?l L. J.,Sinha, Vivek,Kuijpers, Petrus F.,Van Leest, Nicolaas P.,De Bruin, Bas,Demeshko, Serhiy,Siegler, Maxime A.,Van Der Vlugt, Jarl Ivar
supporting information, p. 5117 - 5124 (2017/05/04)
Coordination of FeCl3 to the redox-active pyridine-aminophenol ligand NNOH2 in the presence of base and under aerobic conditions generates FeCl2(NNOISQ) (1), featuring high-spin FeIII and an NNOISQ radical ligand. The complex has an overall S = 2 spin state, as deduced from experimental and computational data. The ligand-centered radical couples antiferromagnetically with the Fe center. Readily available, well-defined, and air-stable 1 catalyzes the challenging intramolecular direct C(sp3)-H amination of unactivated organic azides to generate a range of saturated N-heterocycles with the highest turnover number (TON) (1 mol% of 1, 12 h, TON = 62; 0.1 mol% of 1, 7 days, TON = 620) reported to date. The catalyst is easily recycled without noticeable loss of catalytic activity. A detailed kinetic study for C(sp3)-H amination of 1-azido-4-phenylbutane (S1) revealed zero order in the azide substrate and first order in both the catalyst and Boc2O. A cationic iron complex, generated from the neutral precatalyst upon reaction with Boc2O, is proposed as the catalytically active species.
Cobalt-Porphyrin-Catalysed Intramolecular Ring-Closing C?H Amination of Aliphatic Azides: A Nitrene-Radical Approach to Saturated Heterocycles
Kuijpers, Petrus F.,Tiekink, Martijn J.,Breukelaar, Willem B.,Broere, Dani?l L. J.,van Leest, Nicolaas P.,van der Vlugt, Jarl Ivar,Reek, Joost N. H.,de Bruin, Bas
supporting information, p. 7945 - 7952 (2017/06/19)
Cobalt-porphyrin-catalysed intramolecular ring-closing C?H bond amination enables direct synthesis of various N-heterocycles from aliphatic azides. Pyrrolidines, oxazolidines, imidazolidines, isoindolines and tetrahydroisoquinoline can be obtained in good to excellent yields in a single reaction step with an air- and moisture-stable catalyst. Kinetic studies of the reaction in combination with DFT calculations reveal a metallo-radical-type mechanism involving rate-limiting azide activation to form the key cobalt(III)-nitrene radical intermediate. A subsequent low barrier intramolecular hydrogen-atom transfer from a benzylic C?H bond to the nitrene-radical intermediate followed by a radical rebound step leads to formation of the desired N-heterocyclic ring products. Kinetic isotope competition experiments are in agreement with a radical-type C?H bond-activation step (intramolecular KIE=7), which occurs after the rate-limiting azide activation step. The use of di-tert-butyldicarbonate (Boc2O) significantly enhances the reaction rate by preventing competitive binding of the formed amine product. Under these conditions, the reaction shows clean first-order kinetics in both the [catalyst] and the [azide substrate], and is zero-order in [Boc2O]. Modest enantioselectivities (29–46 % ee in the temperature range of 100–80 °C) could be achieved in the ring closure of (4-azidobutyl)benzene using a new chiral cobalt-porphyrin catalyst equipped with four (1S)-(?)-camphanic-ester groups.
Metal-organic layers stabilize earth-abundant metal-terpyridine diradical complexes for catalytic C-H activation
Lin, Zekai,Thacker, Nathan C.,Sawano, Takahiro,Drake, Tasha,Ji, Pengfei,Lan, Guangxu,Cao, Lingyun,Liu, Shubin,Wang, Cheng,Lin, Wenbin
, p. 143 - 151 (2018/01/02)
We report the synthesis of a terpyridine-based metal-organic layer (TPY-MOL) and its metalation with CoCl2 and FeBr2 to afford CoCl2·TPY-MOL and FeBr2·TPY-MOL, respectively. Upon activation with NaEt3
One-Pot Three-Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination
Orcel, Ugo,Waser, Jerome
supporting information, p. 12881 - 12885 (2016/10/04)
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.
SYNTHESIS OF ACYCLIC AND CYCLIC AMINES USING IRON-CATALYZED NITRENE GROUP TRANSFER
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Paragraph 00163, (2014/09/16)
The present invention provides novel synthetic methods for making acyclic secondary amines by reacting an azide with a compound bearing one or more C-H groups, catalyzed by a FeII-dipyrromethene complex. The acyclic secondary amines are thought
