- Rhodium(III)-Catalyzed Enantio- and Diastereoselective C?H Cyclopropylation of N-Phenoxylsulfonamides: Combined Experimental and Computational Studies
-
Cyclopropane rings are a prominent structural motif in biologically active molecules. Enantio- and diastereoselective construction of cyclopropanes through C?H activation of arenes and coupling with readily available cyclopropenes is highly appealing but
- Zheng, Guangfan,Zhou, Zhi,Zhu, Guoxun,Zhai, Shuailei,Xu, Huiying,Duan, Xujing,Yi, Wei,Li, Xingwei
-
supporting information
p. 2890 - 2896
(2020/01/24)
-
- Synthesis of ortho-phenolic sulfilimines via an intermolecular sulfur atom transfer cascade reaction
-
To expand the toolbox for the synthesis of ortho-phenolic sulfilimines, sigmatropic rearrangements were introduced to the field of sulfilimine chemistry. Herein we report a N-H sulfenylation/[2,3]-sigmatropic rearrangement cascade reaction. This mild reaction enables commercially available thiols to serve as the sulfenylation reagent and generates water as the sole byproduct. Moreover, the reaction has a wide substrate scope and can be conducted on a gram scale with excellent reaction efficiency.
- Ren, Yan,Song, Yinan,Xiong, Feng,Xu, Shaojian,Zhang, Linxing,Zhang, Xinhao,Zuo, Yingying
-
supporting information
p. 3799 - 3803
(2020/06/08)
-
- Dual Directing-Groups-Assisted Redox-Neutral Annulation and Ring Opening of N-Aryloxyacetamides with 1-Alkynylcyclobutanols via Rhodium(III)-Catalyzed C-H/C-C Activations
-
A cascade [3 + 2] annulation and ring opening of N-aryloxyacetamides with 1-alkynylcyclobutanols via Rh(III)-catalyzed redox-neutral C-H/C-C activations using internal oxidative O-NHAc and -OH as the dual directing groups has been achieved. This reaction provided an efficient and regioselective approach to benzofuran derivatives with good functional group compatibility and high yields.
- Pan, Jin-Long,Liu, Chang,Chen, Chao,Liu, Tuan-Qing,Wang, Man,Sun, Zhenliang,Zhang, Shu-Yu
-
supporting information
p. 2823 - 2827
(2019/04/30)
-
- An internal oxidant-directing strategy enabling transition metal-free C–S bond ligation
-
Organic sulfur compounds have broad applications in biology, medicine and material sciences and intensive efforts have been devoted to developing mild and general C–S bond-forming methods. However, a mild, transition-metal-free, direct C–H bond functionalization method remains elusive. Here, we report the use of an internal oxidant-directing strategy to achieve this goal. The cascade reactions described here show excellent chemoselectivity and a wide substrate scope for both oxyamines and sulfenylation reagents. This study enlarges the synthesis toolbox for preparing structurally diverse sulfilimines under mild conditions.
- Zuo, Yingying,Xiong, Feng,Zhao, Jing
-
supporting information
p. 4174 - 4179
(2019/05/24)
-
- Rhodium(III)-catalysed cascade [3 + 2] annulation of: N -aryloxyacetamides with 3-(hetero)arylpropiolic acids: Synthesis of benzofuran-2(3 H)-ones
-
Herein, a cascade [3 + 2] annulation of N-aryloxyacetamides with 3-(hetero)arylpropiolic acids affording benzofuran-2(3H)-ones via rhodium(iii)-catalyzed redox-neutral C-H functionalization/isomerization/lactonization using an internal oxidative directing group O-NHAc was achieved. This catalytic system provides a regio- and stereoselective approach to synthesize (Z)-3-(amino(aryl)methylene)benzofuran-2(3H)-ones with exclusive Z configuration selectivity, acceptable yields and good functional group tolerance. Preliminary investigations on ultraviolet-visible and fluorescence behaviors reveal that the annulation products may be applied as a promising fluorescent probe for sensing metal cations, especially for cerium (Ce3+).
- Pan, Jin-Long,Liu, Tuan-Qing,Chen, Chao,Li, Quan-Zhe,Jiang, Wei,Ding, Tong-Mei,Yan, Zhi-Qiang,Zhu, Guo-Dong
-
supporting information
p. 8589 - 8600
(2019/10/02)
-
- Rh(III)-Catalyzed Redox-Neutral Unsymmetrical C-H Alkylation and Amidation Reactions of N-Phenoxyacetamides
-
A Rh(III)-catalyzed unsymmetrical C-H alkylation and amidation of N-phenoxyacetamides with diazo compounds has been developed under mild and redox-neutral conditions, producing dinitrogen as the only byproduct. The reaction represents the first example of one-step, unsymmetrical difunctionalization of two ortho-C-H bonds. Experimental and computational studies support that N-phenoxyacetamides most likely undergo an initial ortho-C-H alkylation with diazo compounds via a Rh(III)-catalyzed C-H activation, and the resulting Rh(III) intermediate subsequently undergoes an intramolecular oxidative addition into the O-N bond to form a Rh(V) nitrenoid species that is protonated and further directed toward electrophilic addition to the second ortho position of the phenyl ring. This work might provide a new direction for unsymmetrical C-H difunctionalization reactions in an efficient manner.
- Wu, Yunxiang,Chen, Zhaoqiang,Yang, Yaxi,Zhu, Weiliang,Zhou, Bing
-
supporting information
p. 42 - 45
(2018/01/17)
-
- Combination of Cp*RhIII-Catalyzed C?H Activation and a Wagner–Meerwein-Type Rearrangement
-
A combination of Cp*RhIII-catalyzed C?H activation and Wagner–Meerwein-type rearrangement was successfully achieved for the first time. Thus, bridged polycyclic molecules that are not readily accessible by other means were accessed under mild c
- Wang, Xiaoming,Lerchen, Andreas,Gensch, Tobias,Knecht, Tobias,Daniliuc, Constantin G.,Glorius, Frank
-
supporting information
p. 1381 - 1384
(2017/01/24)
-
- Enantioselective Synthesis of Chiral Oxime Ethers: Desymmetrization and Dynamic Kinetic Resolution of Substituted Cyclohexanones
-
Axially chiral cyclohexylidene oxime ethers exhibit unique chirality because of the restricted rotation of C=N. The first catalytic enantioselective synthesis of novel axially chiral cyclohexylidene oximes has been developed by catalytic desymmetrization of 4-substituted cyclohexanones with O-arylhydroxylamines and is catalyzed by a chiral BINOL-derived strontium phosphate with excellent yields and good enantioselectivities. In addition, chiral BINOL-derived phosphoric acid catalyzed dynamic kinetic resolution of α-substituted cyclohexanones has been performed and yields versatile intermediates in high yields and enantioselectivities.
- Nimmagadda, Sri Krishna,Mallojjala, Sharath Chandra,Woztas, Lukasz,Wheeler, Steven E.,Antilla, Jon C.
-
supporting information
p. 2454 - 2458
(2017/02/23)
-
- Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C?H Activation
-
A Cp*RhIII-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C?H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center i
- Li, Yang,Tang, Yuhai,He, Xin,Shi, Dandan,Wu, Jun,Xu, Silong
-
supporting information
p. 7453 - 7457
(2017/06/06)
-
- Cp?Rh(III)/Bicyclic Olefin Cocatalyzed C-H Bond Amidation by Intramolecular Amide Transfer
-
A bicyclic olefin was discovered as a cocatalyst in a Cp?Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C-H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.
- Wang, Xiaoming,Gensch, Tobias,Lerchen, Andreas,Daniliuc, Constantin G.,Glorius, Frank
-
supporting information
p. 6506 - 6512
(2017/05/17)
-
- Synthesis of Functionalized 2-(4-Hydroxyphenyl)-3-methylbenzofuran Allosteric Modulators of Hsp90 Activity
-
Hsp90 is a molecular chaperone that plays a pivotal role in the cell life cycle. ATP-regulated internal dynamics are critical to Hsp90 function and we recently demonstrated that these dynamics can be modulated in an allosteric fashion; the protein C-terminal domain (CTD) can be effectively targeted with a family of 2-phenyl-benzofuran derivatives. Here we describe the expansion of the initial library, reporting 28 new derivatives that explore the chemical space at opposite ends of the benzofuran scaffold. Interactions of the compounds with a full-length protein homolog were explored by Saturation Transfer Difference (STD) NMR spectroscopy. In this context we also report the interaction epitope of Novobiocin, a known CTD inhibitor.
- Sattin, Sara,Panza, Matteo,Vasile, Francesca,Berni, Francesca,Goti, Giulio,Tao, Jiahui,Moroni, Elisabetta,Agard, David,Colombo, Giorgio,Bernardi, Anna
-
supporting information
p. 3349 - 3364
(2016/07/26)
-
- Acylation of Csp2-H bond with acyl sources derived from alkynes: Rh-Cu bimetallic catalyzed CC bond cleavage
-
A Rh-Cu bimetallic catalyzed o-acylation of acyloxacetamide with alkynes has been described. This transformation provides a novel, concise way to synthesize ortho-acylphenols using functionalized alkynes as acylating reagents. Mechanistic studies revealed a Rh-Cu relay process, in which O2 plays a critical role for the formation of carbonyl compounds.
- Xie, Ying
-
supporting information
p. 12372 - 12375
(2016/10/22)
-
- Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes
-
Herein, we report an unprecedented regioselective and entirely atom-economic cobalt(III)-catalyzed method for the non-annulative, intermolecular carboamination of alkenes. The methodology enables the direct synthesis of unnatural amino acid derivatives an
- Lerchen, Andreas,Knecht, Tobias,Daniliuc, Constantin G.,Glorius, Frank
-
supporting information
p. 15166 - 15170
(2016/11/25)
-
- Rh(iii)-catalyzed and alcohol-involved carbenoid C-H insertion into N-phenoxyacetamides using α-diazomalonates
-
Here we report a new and mild Rh(iii)-catalyzed and alcohol-involved carbenoid C-H insertion into N-phenoxyacetamides using α-diazomalonates. This reaction provided a straightforward way for installing both an α-quaternary carbon center and a free-OH moiety into the phenyl ring, thus giving access to useful 2-(2-hydroxyphenyl)-2-alkoxymalonates with good substrate/functional group tolerance. This journal is
- Zhou, Jie,Shi, Jingjing,Liu, Xuelei,Jia, Jinlong,Song, Huacan,Xu, H. Eric,Yi, Wei
-
supporting information
p. 5868 - 5871
(2015/03/30)
-
- Rhodium(iii)-catalyzed C-H activation/[4+3] annulation of N-phenoxyacetamides and α,β-unsaturated aldehydes: An efficient route to 1,2-oxazepines at room temperature
-
An efficient Rh(iii)-catalyzed coupling reaction of N-phenoxyacetamides with α,β-unsaturated aldehydes to give 1,2-oxazepines via C-H activation/[4+3] annulation has been developed. This transformation does not require oxidants and features C-C/C-N bond formation to yield seven-membered oxazepine rings at room temperature. Further derivation of 1,2-oxazepines leads to important chroman derivatives. This journal is
- Duan, Pingping,Lan, Xia,Chen, Ying,Qian, Shao-Song,Li, Jie Jack,Lu, Liang,Lu, Yanbo,Chen, Bo,Hong, Mei,Zhao, Jing
-
supporting information
p. 12135 - 12138
(2014/12/11)
-
- Scalable, transition-metal-free direct oxime o-arylation: Rapid access to o-arylhydroxylamines and substituted benzo[b]furans
-
O-Aryloximes, generated from readily available and inexpensive oximes through transition-metal-free O-arylation, can either be hydrolyzed to O-arylhydroxylamines or conveniently converted to structurally diverse benzo[b]furans through an environmentally benign, one-pot [3,3]-sigmatropic rearrangement/cyclization sequence. A scalable, transition-metal-free (TM-free) direct O-arylation of ketone oximes with a wide range of diaryliodonium salts has been developed. More than two dozen O-arylated oximes have been prepared in good to excellent yields at ambient temperature and were converted to the corresponding substituted benzo[b]furans through a [3,3]-sigmatropic rearrangement/cyclization sequence. Overall, this operationally simple, environmentally benign, and protecting-group-free approach, including a one-pot variant, allows rapid and convenient synthetic access to substituted benzo[b]furans (see scheme).
- Gao, Hongyin,Xu, Qing-Long,Keene, Craig,Kuerti, Laszlo
-
supporting information
p. 8883 - 8887
(2014/07/22)
-
- Copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles via C-H functionalization/C-N/C-O bonds formation
-
A copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles has been developed. The reaction involves a cascade C-H functionalization and C-N/C-O bond formation under oxygen atmosphere.(Figure Presented)
- Guru, Murali Mohan,Ali, Md Ashif,Punniyamurthy, Tharmalingam
-
body text
p. 1194 - 1197
(2011/04/26)
-
- Copper-mediated synthesis of substituted 2-aryl-N-benzylbenzimidazoles and 2-arylbenzoxazoles via C-H functionalization/C-N/C-O bond formation
-
An efficient method for the transformation of N-benzyl bisarylhydrazones and bisaryloxime ethers to functionalized 2-aryl-N-benzylbenzimidazoles and 2-arylbenzoxazoles is described. The protocol involves a copper(II)-mediated cascade C-H functionalization/C-N/C-O bond formation under neutral conditions. Substrates having either electron-donating or -withdrawing substituents undergo the cyclization to afford the target heterocycles at moderate temperature.
- Guru, Murali Mohan,Ali, Md Ashif,Punniyamurthy, Tharmalingam
-
scheme or table
p. 5295 - 5308
(2011/08/05)
-
- Fluorous tagged N-hydroxy phthalimide for the parallel synthesis of O-aryloxyamines
-
The parallel synthesis of O-aryloxyamines remains an unfulfilled need in the field of medicinal chemistry and fragment-based approaches. To fill this gap a solution-phase two-step process based on (1) a copper-catalyzed cross-coupling of aryl boronic acid
- Gaucher-Wieczorek, Florence S.,Maillard, Ludovic T.,Badet, Bernard,Durand, Philippe
-
scheme or table
p. 655 - 658
(2010/10/21)
-
- Direct preparation of benzofurans from O-arylhydroxylamines
-
Reaction of O-arylhydroxylamine hydrochlorides with either cyclic or acyclic ketones in the presence of methanesulfonic acid leads directly to the benzofuran derivative via a proposed one-pot condensation-rearrangement- cyclisation reaction sequence in good to excellent yields. Georg Thieme Verlag Stuttgart.
- Contiero, Fanny,Jones, Kevin M.,Matts, Edward A.,Porzelle, Achim,Tomkinson, Nicholas C.O.
-
scheme or table
p. 3003 - 3006
(2010/03/03)
-
- 9-Cyano-1-azapaullone (Cazpaullone), a Glycogen Synthase Kinase-3 (GSK-3) inhibitor activating pancreatic β cell protection and replication
-
Recently, the serine/threonine kinase glycogen synthase kinase-3 (GSK-3) emerged as a regulator of pancreatic β cell growth and survival. On the basis of the previous observation that GSK-3 inhibitors like 1-azakenpaullone promote β cell protection and re
- Stukenbrock, Hendrik,Mussmann, Rainer,Geese, Marcus,Ferandin, Yoan,Lozach, Olivier,Lemcke, Thomas,Kegel, Simone,Lomow, Alexander,Burk, Ulrike,Dohrmann, Cord,Meijer, Laurent,Austen, Matthias,Kunick, Conrad
-
p. 2196 - 2207
(2008/12/22)
-