57981-18-7Relevant academic research and scientific papers
Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents
Kalra, Anshika,Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Ai, Lin,Sanakis, Yiannis,Raptopoulos, Grigorios,Mohapatra, Sudip,Choudhury, Amitava,Sun, Zhicheng,Cundari, Thomas R.,Stavropoulos, Pericles
, p. 1974 - 1996 (2021/06/28)
Recent research has highlighted the key role played by the electron affinity of the active metal-nitrene/imido oxidant as the driving force in nitrene additions to olefins to afford valuable aziridines. The present work showcases a library of Co(II) reage
Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
supporting information, p. 9729 - 9736 (2021/07/19)
Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs; the newly formed C-I bond in these products is then functionalized via a silyl-mediated Giese reaction. This chemistry also translates smoothly to 1,3-disubstituted iodo-BCPs. A wide variety of radical acceptors and iodo-BCPAs are accommodated, providing straightforward access to an array of valuable aniline-like isosteres.
H-*BEA Zeolite-Catalyzed Nucleophilic Substitution in Allyl Alcohols Using Sulfonamides, Amides, and Anilines
Aoki, Shunsuke,Fujii, Takeshi,Morita, Sachiko,Nishida, Ryo,Ohtsuki, Akimichi,Okumura, Kazu
, (2020/07/24)
Herein, we report a novel zeolite-catalyzed nucleophilic substitution in allyl alcohols. The product yield was improved upon the addition of NaOTf (0.05 mol-percent) using the studied zeolites. The highest yields were observed using H-*BEA(Si/Al2 = 40)/NaOTf. The scope of the reaction with respect to the nucleophile was examined using 1,3-diphenylprop-2-ene-1-ol as a model substrate under optimized reaction conditions. p-Substituted aryl sulfonamides bearing electron-rich or electron-deficient substituents, alkyl sulfonamides, and heteroaryl sulfonamides undergo the amidation reaction to produce their corresponding allyl sulfonamides in good yield. Amides and anilines exhibited low activity under the optimized conditions, however, performing the reaction at 90 °C produced the target product. The scope of the allyl alcohol was investigated using p-toluenesulfonamide as the nucleophile and the reaction proceeded with a variety of allylic alcohols. To probe the practical utility of the H-*BEA-catalyzed amidation reaction, a gram-scale reaction was performed using 1.01 g (4.8 mmol) of allyl alcohol, which afforded the target product in 88 percent yield.
Imino-λ3-iodane and Catalytic Amount of I2-Mediated Synthesis of N-Allylsulfenamides via [2,3]-Sigmatropic Rearrangement
Makitalo, Cody L.,Mironova, Irina A.,Rohde, Gregory T.,Saito, Akio,Yoshimura, Akira,Yusubov, Mekhman S.,Yusubova, Rosa Y.,Zhdankin, Viktor V.
, p. 6433 - 6439 (2020/10/21)
A facile metal-free [2,3]-sigmatropic rearrangement reaction of allyl sulfides via N-sulfilimine intermediates has been developed. Treatment of allyl sulfides with imino-λ3-iodanes in the presence of a catalytic amount of elemental iodine allow
A lutidine-promoted photoredox catalytic atom-transfer radical cyclization reaction for the synthesis of 4-bromo-3,3-dialkyl-octahydro-indol-2-ones
Zhao, Quan-Sheng,Xu, Guo-Qiang,Xu, Ji-Tao,Wang, Zhu-Yin,Xu, Peng-Fei
, p. 2206 - 2209 (2020/02/26)
Reported herein is a visible-light-catalyzed photoredox atom-transfer radical cyclization (ATRC) halo-alkylation of 1,6-dienes with α-halo-ketones as the ATRC reagent. This process exhibits high atom economy, high step economy, and high redox economy, which can directly construct a 4-bromo-3,3-dialkyl-octahydro-indol-2-one core under mild conditions in one pot, and lutidine is found to be the key promoter for this ATRC process.
Formal Bromine Atom Transfer Radical Addition of Nonactivated Bromoalkanes Using Photoredox Gold Catalysis
Zidan, Montserrat,McCallum, Terry,Swann, Rowan,Barriault, Louis
supporting information, p. 8401 - 8406 (2020/11/03)
Organic transformations mediated by photoredox catalysis have been at the forefront of reaction discovery. Recently, it has been demonstrated that binuclear Au(I) bisphosphine complexes, such as [Au2(μ-dppm)2]X2, are capable of mediating electron transfer to nonactivated bromoalkanes for the generation of a variety of alkyl radicals. The transfer reactions of bromine, derived from nonactivated bromoalkanes, are largely unknown. Therefore, we propose that unique metal-based mechanistic pathways are at play, as this binuclear gold catalyst has been known to produce Au(III) Lewis acid intermediates. The scope and proposed mechanistic overview for the formal bromine atom transfer reaction of nonactivated bromoalkanes mediated by photoredox Au(I) catalysis is presented. The methodology presented afforded good yields and a broad scope which include examples using bromoalkanes and iodoarenes.
Cobalt-catalyzed cyclization with the introduction of cyano, acyl and aminoalkyl groups
Hori, Hiroto,Arai, Shigeru,Nishida, Atsushi
, p. 4783 - 4788 (2019/05/24)
An efficient synthesis of carbo-and heterocycles using CC, CO and CN bonds under cobalt catalysis is described. The substituents on olefins are key for controlling the regio-and chemoselectivity in the initial hydrogen atom transfer step and quaternary carbons are efficiently constructed under mild conditions. Cyclopropane cleavage and tandem cyclization give highly functionalized bicyclic skeletons in a single operation.
Highly efficient mesoporous polymer supported phosphine-gold(i) complex catalysts for amination of allylic alcohols and intramolecular cyclization reactions
Gu, Huoliang,Sun, Xiong,Wang, Yong,Wu, Haihong,Wu, Peng
, p. 1737 - 1743 (2018/02/06)
A series of novel heterogeneous gold(i) catalysts were synthesized by immobilizing gold(i) complexes on ordered mesoporous polymer FDU-15 and characterized by XRD, N2 adsorption-desorption, FT-IR, TEM, EDS, etc. The catalytic activities of thes
A Metal–Organic Framework with Exceptional Activity for C?H Bond Amination
Wang, Le,Agnew, Douglas W.,Yu, Xiao,Figueroa, Joshua S.,Cohen, Seth M.
supporting information, p. 511 - 515 (2018/02/21)
The development of catalysts capable of fast, robust C?H bond amination under mild conditions is an unrealized goal despite substantial progress in the field of C?H activation in recent years. A Mn-based metal–organic framework (CPF-5) is described that promotes the direct amination of C?H bonds with exceptional activity. CPF-5 is capable of functionalizing C?H bonds in an intermolecular fashion with unrivaled catalytic stability producing >105 turnovers.
Direct Sulfonamidation of Primary and Secondary Benzylic Alcohols Catalyzed by a Boronic Acid/Oxalic Acid System
Verdelet, Tristan,Ward, Robert M.,Hall, Dennis G.
, p. 5729 - 5738 (2017/10/06)
The direct sulfonamidation of primary and secondary benzylic alcohols catalyzed by a 2,3,4,5-tetrafluorophenylboronic acid/oxalic acid co-catalytic system was examined. The reaction proceeds under mild conditions with readily available starting materials and has been shown to be gram-scalable without significant decrease of yield. Both primary and secondary benzylic alcohols were evaluated and afforded the desired sulfonamide products with good to excellent yields.
