- Rhodium(III)-Catalyzed Aldehyde C?H Activation and Functionalization with Dioxazolones: An Entry to Imide Synthesis
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A rhodium(III)-based catalytic system has been used to develop a C?H bond activation of benzaldehyde derivatives and subsequent functionalization with dioxazolones in order to afford imides. The importance of the nature of the directing group to perform selectively the aldehydic C?H bond activation has been highlighted. The scope investigation showed that this transformation could be applied to various dioxazolones and many benzaldehyde derivatives as well as an acrolein derivative. Derivatization reactions of the imide products demonstrated the synthetic utility of this rhodium-catalyzed aldehydic C?H amidation.
- Massouh, Joe,Petrelli, Antoine,Bellière-Baca, Virginie,Hérault, Damien,Clavier, Hervé
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p. 831 - 837
(2022/01/06)
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- Cu(II)-Catalyzed C-H Amidation/Cyclization of Azomethine Imines with Dioxazolones via Acyl Nitrenes: A Direct Access to Diverse 1,2,4-Triazole Derivatives
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We report a Cu(II)-catalyzed C-H amidation/cyclization of azomethine imines with dioxazolones as acyl nitrene transfer reagents under additive-and ligand-free conditions. An array of 1,2,4-triazolo[1,5-a]pyridine derivatives were afforded in moderate to good yields with excellent functional group tolerance. In addition, scale-up reaction and photoluminescence properties were discussed.
- Liu, Xiang,Li, Wen,Jiang, Wenxuan,Lu, Hao,Liu, Jiali,Lin, Yijun,Cao, Hua
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p. 613 - 618
(2022/01/20)
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- Chemical Upcycling of Waste Poly(bisphenol A carbonate) to 1,4,2-Dioxazol-5-ones and One-Pot C?H Amidation
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Chemical upcycling of poly(bisphenol A carbonate) (PC) was achieved in this study with hydroxamic acid nucleophiles, giving rise to synthetically valuable 1,4,2-dioxazol-5-ones and bisphenol A. Using 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD), non-green carbodiimidazole or phosgene carbonylation agents used in conventional dioxazolone synthesis were successfully replaced with PC, and environmentally harmful bisphenol A was simultaneously recovered. Assorted hydroxamic acids exhibited good-to-excellent efficiencies and green chemical features, promising broad synthetic application scope. In addition, a green aryl amide synthesis process was developed, involving one-pot depolymerization from polycarbonate to dioxazolone followed by rhodium-catalyzed C?H amidation, including gram-scale examples with used compact discs.
- Jung, Hyun Jin,Park, Sora,Lee, Hyun Sub,Shin, Hyun Gyu,Yoo, Yeji,Baral, Ek Raj,Lee, Jun Hee,Kwak, Jaesung,Kim, Jeung Gon
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p. 4301 - 4306
(2021/07/09)
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- Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones
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A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).
- Chen, Qishu,Du, Bingnan,Ouyang, Yuxin,Yu, Wing-Yiu
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p. 14962 - 14968
(2021/09/29)
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- Direct synthesis of benzoxazinones via Cp*Co(III)-catalyzed C–H activation and annulation of sulfoxonium ylides with dioxazolones
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A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(III)-catalyzed C–H activation and [3 + 3] annulation between sulfoxonium ylides and dioxazolones. The reaction is conducted under base-free conditions and tolerates various functional groups. Starting from diverse readily available sulfoxonium ylides and dioxazolones, a variety of benzoxazinones could be synthesized in one step in 32%-75% yields.
- Yu, Yongqi,Xia, Zhen,Wu, Qianlong,Liu, Da,Yu, Lin,Xiao, Yuanjiu,Tan, Ze,Deng, Wei,Zhu, Gangguo
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p. 1263 - 1266
(2020/10/08)
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- Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones
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Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C?H amidations strategies, an intermolecular regioselective C?H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.
- Tang, Jing-Jing,Yu, Xiaoqiang,Wang, Yi,Yamamoto, Yoshinori,Bao, Ming
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supporting information
p. 16426 - 16435
(2021/05/13)
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- Chiral amination sulfoxide and preparation method thereof (by machine translation)
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The invention belongs to the field of organic synthesis, and discloses chiral amination sulfoxide which has the structure of a general formula I. Wherein R is hydrogen or R1 And R2 Each independently selected from one of the following structures: hydrogen, alkyl, alkoxy, ester, trifluoromethyl, trifluoromethoxy, trifluoromethylthio. Halogens, alkynyl groups, alkenyl groups, amino groups, cyano groups, hydroxyl groups, aldehyde groups, carboxyl groups, nitro groups, amide groups, benzene rings, and bonded benzene ring fused rings to naphthalene; R3 Selected from the group consisting of phenyl, optionally substituted phenyl, aryl, heteroaryl, styryl, alkyl, haloalkyl and the like. The method comprises the following steps: forming a complex with a tert-butyl cyclopentadienyl metal iridium complex, forming a complex with the modified chiral proline, and activating C-H bond of enantioselective induced sulfoxide to obtain chiral sulphoxide. The synthetic method disclosed by the invention is high in yield and good in enantioselectivity, and the obtained amidated sulfoxide can be derivatized to obtain a chiral ligand. (by machine translation)
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Paragraph 0245; 0257-0259; 0260-0262; 0269-0271
(2020/11/12)
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- Co(III)-Catalyzed C-H Amidation of Nitrogen-Containing Heterocycles with Dioxazolones under Mild Conditions
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A cobalt(III)-catalyzed C-8 selective C-H amidation of quinoline N-oxide using dioxazolone as an amidating reagent under mild conditions is disclosed. The reaction proceeds efficiently with excellent functional group compatibility. The utility of the current method is demonstrated by gram scale synthesis of C-8 amide quinoline N-oxide and by converting this amidated product into functionalized quinolines. Furthermore, the developed catalytic method is also applicable for C-7 amidation of N-pyrimidylindolines and ortho-amidation of benzamides.
- Dhiman, Ankit Kumar,Thakur, Ankita,Kumar, Inder,Kumar, Rakesh,Sharma, Upendra
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p. 9244 - 9254
(2020/08/14)
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- Rhodium(III)-catalyzed C4-amidation of indole-oximes with dioxazolones: Via C-H activation
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A novel method for the Rh(III)-catalyzed oxime-directed C-H amidation of indoles with dioxazolones has been developed. This strategy provides an exclusive site selectivity and the directing group can be easily removed. This transformation features a wide substrate scope, good functional group tolerance and excellent yields, and may serve as a significant tool to construct structurally diverse indole derivatives for the screening of potential pharmaceuticals in the future. This journal is
- Deng, Ke-Zuan,Fu, Xiao-Pan,Ji, Ya-Fei,Tang, Shi-Biao,Wu, Gao-Rong,Xia, Cheng-Cai,Yang, Jin-Yue,Zhang, Li-Li
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p. 7922 - 7931
(2020/11/02)
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- Ketone-Directed Cobalt(III)-Catalyzed Regioselective C2 Amidation of Indoles
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An efficient cobalt(III)-catalyzed method for the direct C-H amidation of unprotected indoles for 2-amino indole scaffold construction has been developed. With dioxazolone as the amidating reagent, a variety of 2-amino indole derivatives were achieved in moderate to excellent yields using an organic acid as the additive and a ketone as the directing group.
- Shi, Xinxia,Xu, Weiyan,Wang, Rongchao,Zeng, Xiaofei,Qiu, Huayu,Wang, Min
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p. 3911 - 3920
(2020/03/23)
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- Rhodium(iii)-catalyzed diamidation of olefins: Via amidorhodation and further amidation
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Rh(iii)-catalyzed synthesis of vicinal diamides has been realized via elaboration of an authenticated Rh-C(sp3) species generated via initial intramolecular amidorhodation of olefins. The second amidation was achieved using both electrophilic and nucleophilic amidating reagents. The reactions proceeded under mild conditions with good yield, broad substrate scope, and excellent functional-group tolerance.
- Wang, Jinlei,Zheng, Guangfan,Li, Xingwei
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supporting information
p. 7809 - 7812
(2020/07/27)
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- Cp*Co(III)-catalyzed C[sbnd]H amidation of azines with dioxazolones
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Cp*Co(III)-catalyzed direct C[sbnd]H amidation of azines has been developed. This conversion could proceed smoothly in the absence of external oxidants, acids or bases, with excellent regioselectivity and broad functional group tolerance. CO2 w
- Huang, Yanzhen,Pi, Chao,Tang, Zhen,Wu, Yangjie,Cui, Xiuling
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supporting information
p. 3237 - 3240
(2020/09/15)
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- Dioxazolones as masked ester surrogates in the Pd(ii)-catalyzed direct C-H arylation of 6,5-fused heterocycles
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A simple and effective Pd(ii)-catalyzed regioselective C(2)-H arylation of 6,5-fused heterocycles with dioxazolones as a masked ester surrogate under mild conditions is reported. The significance of the arylation is highlighted by the new reactivity demonstrated in dioxazolones via proximal C-H activation of the cyclic carbonate of the hydroxamic acid functionality under protic conditions.
- Saxena, Paridhi,Maida, Neha,Kapur, Manmohan
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p. 11187 - 11190
(2019/09/30)
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- Rhodium(iii)-catalyzed cascade reactions of benzoic acids with dioxazolones: Discovery of 2,5-substituted benzoxazinones as AIE molecules
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A rhodium-catalyzed cascade reaction of benzoic acids with 1,4,2-dioxazol-5-ones was studied. The carboxyl group enabled a double C-H amidation followed by further intramolecular cyclization to afford 2,5-substituted benzoxazinones, which exhibited aggregation-induced emission (AIE) properties with a promising excited-state intramolecular proton-transfer (ESIPT) phenomenon.
- Li, Jinbiao,Zhang, Shuaizhong,Lonka, Madhava Reddy,Zhang, Jinquan,Zou, Hongbin
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supporting information
p. 11203 - 11206
(2019/09/30)
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- Cobalt-Catalyzed Ortho-C(sp2)-H Amidation of Benzaldehydes with Dioxazolones Using Transient Directing Groups
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An efficient and convenient cobalt-catalyzed ortho-C(sp2)-H amidation of benzaldehydes employing dioxazolones as the aminating reagent has been developed. The key feature of this protocol is the use of green and economic earth-abundant metals c
- Huang, Jie,Ding, Jun,Ding, Tong-Mei,Zhang, Shuiyi,Wang, Yaqiu,Sha, Feng,Zhang, Shu-Yu,Wu, Xin-Yan,Li, Qiong
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p. 7342 - 7345
(2019/10/02)
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- Synthesis of isoquinolone via rhodium(III)-catalyzed C-H activation with 1,4,2-dioxazol-5-ones as oxidizing directing group
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An efficient rhodium-catalyzed direct C-H activation for the synthesis of isoquinolone with 1,4,2-dioxazol-5-ones as oxidizing directing groups have been developed, which featured mild reaction conditions, short reaction time and satisfactory yield.
- Zhu, Huajian,Zhuang, Rangxiao,Zheng, Wenya,Fu, Liping,Zhao, Yuanke,Tu, Luping,Chai, Yitao,Zeng, Linghui,Zhang, Chong,Zhang, Jiankang
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p. 3108 - 3112
(2019/05/08)
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- Efficient Copper-Catalyzed Multicomponent Synthesis of N-Acyl Amidines via Acyl Nitrenes
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Direct synthetic routes to amidines are desired, as they are widely present in many biologically active compounds and organometallic complexes. N-Acyl amidines in particular can be used as a starting material for the synthesis of heterocycles and have several other applications. Here, we describe a fast and practical copper-catalyzed three-component reaction of aryl acetylenes, amines, and easily accessible 1,4,2-dioxazol-5-ones to N-acyl amidines, generating CO2 as the only byproduct. Transformation of the dioxazolones on the Cu catalyst generates acyl nitrenes that rapidly insert into the copper acetylide Cu-C bond rather than undergoing an undesired Curtius rearrangement. For nonaromatic dioxazolones, [Cu(OAc)(Xantphos)] is a superior catalyst for this transformation, leading to full substrate conversion within 10 min. For the direct synthesis of N-benzoyl amidine derivatives from aromatic dioxazolones, [Cu(OAc)(Xantphos)] proved to be inactive, but moderate to good yields were obtained when using simple copper(I) iodide (CuI) as the catalyst. Mechanistic studies revealed the aerobic instability of one of the intermediates at low catalyst loadings, but the reaction could still be performed in air for most substrates when using catalyst loadings of 5 mol %. The herein reported procedure not only provides a new, practical, and direct route to N-acyl amidines but also represents a new type of C-N bond formation.
- Van Vliet, Kaj M.,Polak, Lara H.,Siegler, Maxime A.,Van Der Vlugt, Jarl Ivar,Guerra, Célia Fonseca,De Bruin, Bas
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supporting information
p. 15240 - 15249
(2019/10/19)
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- Experimental and computational studies on H2O-promoted, Rh-catalyzed transient-ligand-free ortho-C(sp2)-H amidation of benzaldehydes with dioxazolones
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An efficient and convenient ligand-free, rhodium-catalyzed ortho-C(sp2)-H amidation of benzaldehydes with dioxazolones using H2O as the key promoter is described. Using this protocol, a wide range of benzaldehyde substrates were selectively amidated in good to excellent yields with broad functional group compatibility. KIE experiments revealed that the C-H bond activation was likely the rate-limiting step. In addition, computational studies indicated that the catalyst precursor interacted with water and dioxazolones to generate the active catalytic species. Notably, the practicality and efficacy of this method were illustrated by a late-stage amidation of an estrone-derived molecule and further transformations of the amidated product.
- Ding, Jun,Jiang, Wei,Bai, He-Yuan,Ding, Tong-Mei,Gao, Dafang,Bao, Xiaoguang,Zhang, Shu-Yu
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p. 8889 - 8892
(2018/08/17)
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- Rh-Catalyzed Annulation of ortho-C?H Bonds of 2-Arylimidazoles with 1,4,2-Dioxazol-5-ones toward 5-Arylimidazo[1,2-c]quinazolines
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A Rh-catalyzed unique and direct approach for constructing a series of 5-arylimidazo[1,2-c]quinazolines in moderate to excellent yields from simple and readily available 2-arylimidazoles and 3-phenyl-1,4,2-dioxazol-5-ones was described. This procedure pro
- Wu, Xiaopeng,Sun, Song,Xu, Shengbo,Cheng, Jiang
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supporting information
p. 1111 - 1115
(2018/01/27)
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- Co(III)-Catalyzed Enaminone-Directed C-H Amidation for Quinolone Synthesis
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We report herein the development of a Co(III)-catalyzed enaminone-directed C-H amidation method for synthetic access to quinolones, an important heterocyclic scaffold for diverse pharmaceutically active structures. The C-H coupling with dioxazolones and subsequent deacylation of an installed amide group allow consecutive C-N coupling generation of quinolones with wide-ranging compatible substituent patterns.
- Shi, Pengfei,Wang, Lili,Chen, Kehao,Wang, Jie,Zhu, Jin
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supporting information
p. 2418 - 2421
(2017/05/12)
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- Rhodium(III)-Catalyzed Directed C?H Amidation of N-Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles
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An efficient rhodium-catalyzed direct C?H amidation of N-nitrosoanilines with 1,4,2-dioxazol-5-ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2-disubstituted benzimidazoles via an HCl-mediated deprotection/cyclization process in one pot.
- Chen, Yanyu,Zhang, Rong,Peng, Qiujun,Xu, Lanting,Pan, XianHua
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supporting information
p. 2804 - 2808
(2017/10/20)
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- Rh(III)- and Zn(II)-Catalyzed Synthesis of Quinazoline N-Oxides via C-H Amidation-Cyclization of Oximes
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Quinazoline N-oxides have been prepared from simple ketoximes and 1,4,2-dioxazol-5-ones via Rh(III)-catalyzed C-H activation-amidation of the ketoximes and subsequent Zn(II)-catalyzed cyclization. The substrate scope and functional group compatibility were examined. The reaction features relay catalysis by Rh(III) and Zn(II).
- Wang, Qiang,Wang, Fen,Yang, Xifa,Zhou, Xukai,Li, Xingwei
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supporting information
p. 6144 - 6147
(2016/12/09)
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- Site-Selective C–H Amidation of Azobenzenes with Dioxazolones under Rhodium Catalysis
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The rhodium(III)-catalyzed amidation reaction of azobenzenes with dioxazolones is described. This strategy allows the facile and efficient construction of highly substituted ortho-amidated azobenzenes by direct C–H cleavage approach. A wide range of substrates, excellent levels of chemoselectivity as well as high functional-group tolerance were observed. In addition, this protocol was used to generate an array of ortho-amidated ketazines. Further synthetic transformation of amidated azobenzenes furnished a facile construction of benzimidazole and benzotriazole derivatives.
- Mishra, Neeraj Kumar,Oh, Yongguk,Jeon, Mijin,Han, Sangil,Sharma, Satyasheel,Han, Sang Hoon,Um, Sung Hee,Kim, In Su
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supporting information
p. 4976 - 4980
(2016/10/26)
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- Mechanistic Studies on the Rh(III)-Mediated Amido Transfer Process Leading to Robust C-H Amination with a New Type of Amidating Reagent
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Mechanistic investigations on the CpRh(III)-catalyzed direct C-H amination reaction led us to reveal the new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis on the C-N bond-forming process showed th
- Park, Yoonsu,Park, Kyung Tae,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 4534 - 4542
(2015/04/22)
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