- Facile synthesis, antimicrobial and antiviral evaluation of novel substituted phenyl 1,3-thiazolidin-4-one sulfonyl derivatives
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A series of novel substituted phenyl 1, 3-thiazolidin-4-one sulfonyl derivatives 5 (a-t) were synthesized and screened for their in-vitro anti-microbial and anti-viral activity. The result of the anti-microbial assay demonstrated compounds 5d, 5f, 5g, 5h,
- Mandal, Milan Kumar,Ghosh, Swagatika,Naesens, Lieve,Bhat, Hans Raj,Singh, Udaya Pratap
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- Mild Darzens Annulations for the Assembly of Trifluoromethylthiolated (SCF3) Aziridine and Cyclopropane Structures
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We report mild new annulation approaches to trisubstituted trifluoromethylthiolated (SCF3) aziridines and cyclopropanes via Darzens inspired protocols. The products of these anionic annulations, rarely studied previously, possess attractive features rendering them valuable building blocks for synthesis platforms. In this study, trisubstituted acetophenone nucleophiles bearing SCF3 and bromine substituents in their α position were shown to undergo [2 + 1] annulations with vinyl ketones and tosyl-protected imines under mild reaction conditions.
- Delost, Michael D.,Njardarson, Jon T.
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supporting information
p. 6121 - 6125
(2021/08/16)
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- Accelerated Reactivity Mechanism and Interpretable Machine Learning Model of N-Sulfonylimines toward Fast Multicomponent Reactions
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We introduce chemical reactivity flowcharts to help chemists interpret reaction outcomes using statistically robust machine learning models trained on a small number of reactions. We developed fast N-sulfonylimine multicomponent reactions for understanding reactivity and to generate training data. Accelerated reactivity mechanisms were investigated using density functional theory. Intuitive chemical features learned by the model accurately predicted heterogeneous reactivity of N-sulfonylimine with different carboxylic acids. Validation of the predictions shows that reaction outcome interpretation is useful for human chemists.
- Jethava, Krupal P.,Fine, Jonathan,Chen, Yingqi,Hossain, Ahad,Chopra, Gaurav
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supporting information
p. 8480 - 8486
(2020/11/18)
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- The diastereoselective synthesis of 2,3-diaryl-3-cyano-substituted pyrrolidines via the MgI2 mediated ring expansion of aryl cyclopropyl nitriles
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The MgI2 mediated reaction of aryl substituted cyclopropyl nitriles with tosyl aldimines to give 2,3-diaryl-3-cyano-substituted pyrrolidines has been demonstrated. In all cases, the trans-diastereoisomer was determined to be the major product.
- Stead, Darren
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supporting information
(2020/09/04)
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- Strategic vinyl sulfone nucleophile β-substitution significantly impacts selectivity in Vinylogous Darzens and aza-Darzens reactions
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Vinylogous Darzens and aza-Darzens reactions employing a benzothiophene 1,1-dioxide nucleophile are reported. These new [2 + 1] annulation reactions, which proceed under mild reaction conditions, are γ-selective, affording trans-epoxides selectively and favoring trans-aziridines. The reactions are base-dependent, with KOtBu and Cs2CO3 being optimal for aldehyde and imine annulations, respectively. Comparison of the benzothiophene nucleophile to its acyclic counterpart reveals superior performance in the case of aldehydes, while the outcome varies depending on the sulfonamide imine used.
- Delost, Michael D.,Njardarson, Jon T.
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supporting information
p. 6917 - 6921
(2020/09/12)
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- Iron-based nanomaterials used as magnetic mesoporous nanocomposites to catalyze the preparation of N-sulfonylimines
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A new magnetic nanocatalyzed synthetic method for the synthesis of aldimines was evidenced. The reaction was carried out in a Schlenk tube under reflux conditions using various solvents and different nanomaterials as catalysts. In these reactions, an exce
- Ashouri, Akram,Samadi, Saadi,Nasiri, Behzad,Bahrami, Zohre
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p. 549 - 556
(2019/08/01)
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- Silica-supported zinc chloride (ZnCl2/SiO2)-induced efficient protocol for the synthesis of N-sulfonyl imines and 2-Arylbenzothiazole
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A straightforward strategy for the synthesis of N-sulfonyl imine derivatives from sulfonamides and aryl aldehydes utilizing Silica-supported zinc chloride (ZnCl2/SiO2, silzic) as a catalyst under solvent-free conditions has been developed. 2-Arylbenzothiazole derivatives were also synthesized by the reaction of 2-aminothiophenol with aryl aldehydes under the same conditions. This procedure has advantages of high yields, mild reaction condition, simple procedure, low cost, and simplicity of workup. The catalyst has the same efficiency on its reuse up to three times.
- Soliman, Hanan A.,El-Shahat, Mahmoud,Soliman, Abdel-Ghany
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p. 584 - 591
(2019/07/31)
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- Ruthenium-Catalyzed Synthesis of Isoindolinones via Amide-Directed Addition of Aromatic C-H Bonds to Aldimines
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Ruthenium-catalyzed addition of aromatic C-H bonds to aldimines is described. [RuCl2(p-cymene)]2 functions as an efficient catalyst to promote the coupling of aryl amides with aldimines in the presence of a catalytic amount of base to give the corresponding isoindolinone derivatives. The nature of the substituent at the N-atom of the amides is crucial for the efficient conversion of the substrates, and a p-toluenesulfonyl group is the functionality of choice. A variety of amides and aldimines participated in the present Ru-catalyzed reaction to furnish the corresponding isoindolinones in moderate to high yield.
- Miura, Hiroki,Kimura, Yuriko,Terajima, Sachie,Shishido, Tetsuya
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supporting information
p. 2807 - 2811
(2019/02/01)
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- Enantioselective Aza-Reformatsky Reaction with Ketimines
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Here, an enantioselective aza-Reformatsky reaction using acyclic ketimine substrates is presented. Using α-phosphorated ketimines as electrophilic substrates and a simple BINOL-derived ligand, phosphorated analogues of aspartic acid holding chiral tetrasubstituted carbons are efficiently obtained with excellent enantioselectivity through an asymmetric organocatalytic Reformatsky-type reaction. The phosphorated analogues of aspartic acid have been used for the synthesis of phosphorus-containing enantiopure tetrasubstituted β-lactams.
- Maestro, Aitor,Martinez De Marigorta, Edorta,Palacios, Francisco,Vicario, Javier
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supporting information
p. 9473 - 9477
(2019/11/28)
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- Practical N-hydroxyphthalimide-mediated oxidation of sulfonamides to N-sulfonylimines
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A new method to prepare sulfonylimines through the oxidation of sulfonamides mediated by N-hydroxyphthalimide under mild conditions has been developed. Compared to reported oxidation methods, broader substrates scope and milder conditions were achieved in
- Wang, Jian,Yi, Wen-Jing
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- Rh(III)-Catalyzed [3 + 2] Annulation via C-H Activation: Direct Access to Trifluoromethyl-Substituted Indenamines and Aminoindanes
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The rhodium(III)-catalyzed direct C-H addition and annulation of benzimidates and aldimines with β-(trifluoromethyl)-α,β-unsaturated ketones is described. This protocol provides the facile and efficient formation of various trifluoromethyl-containing inde
- Chaudhary, Bharatkumar,Auti, Prashant,Shinde, Suchita Dattatray,Yakkala, Prasanna Anjaneyulu,Giri, Deepesh,Sharma, Satyasheel
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supporting information
p. 2763 - 2767
(2019/04/30)
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- Visible-light, iodine-promoted formation of n-sulfonyl imines and n-alkylsulfonamides from aldehydes and hypervalent iodine reagents
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Alternative synthetic methodology for the direct installation of sulfonamide functionality is a highly desirable goal within the domain of drug discovery and development. The formation of synthetically valuable N-sulfonyl imines from a range of aldehydes,
- Hopkins, Megan D,Brandeburg, Zachary C.,Hanson, Andrew J.,Lamar, Angus A
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- Fe(III)/ l -Valine-Catalyzed One-Pot Synthesis of N -Sulfinyl- and N -Sulfonylimines via Oxidative Cascade Reaction of Alcohols with Sulfinamides or Sulfonamides
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An efficient Fe(III), l -valine, and 4-OH-TEMPO catalytic system was found for the oxidation of alcohols followed by condensation with sulfinamide or sulfonamide in one pot for the synthesis of N -sulfinyl- and N- sulfonylimines compounds under mild conditions. This transformation accommodates a variety of substrates, shows high functional-group tolerance, and affords the corresponding products in good to excellent yields.
- Zhang, Guofu,Xing, Yunzhe,Xu, Shengjun,Ding, Chengrong,Shan, Shang
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supporting information
p. 1232 - 1238
(2018/03/23)
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- Developments in the Reactivity of 2-Methylimidazolium Salts
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Unexpected and unusual reactivity of 2-methylimidazolium salts toward aryl-N-sulfonylimines and aryl aldehydes is here reported. Upon reaction with aryl-N-sulfonylimines, the addition product, arylethyl-2-imidazolium-1-tosylamide (3), is formed with moderate to good yields, while upon reaction with aldehydes, the initial addition product (6) observed in NMR and HPLC-MS experimental analysis is postulated by us as an intermediate to the final conversion to carboxylic acids. Studies in the presence and absence of molecular oxygen allow us to conclude that the imidazolium salts is crucial for the oxidation. A detailed mechanistic study was carried out to provide insights regarding this unexpected reactivity.
- Peixoto, Daniela,Figueiredo, Margarida,Gawande, Manoj B.,Corvo, Marta C.,Vanhoenacker, Gerd,Afonso, Carlos A.M.,Ferreira, Luisa M.,Branco, Paula S.
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p. 6232 - 6241
(2017/06/23)
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- Palladium-Catalyzed Direct Intramolecular C-N Bond Formation: Access to Multisubstituted Dihydropyrroles
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A palladium-catalyzed intramolecular amination of alkenes with retention of olefin functionalization was achieved under mild reaction conditions. In the presence of palladium catalyst, the tosyl-protected amine can directly couple with a double bond to provide versatile dihydropyrrole derivatives in moderate to excellent yields.
- Jiang, Bing,Meng, Fei-Fan,Liang, Qiu-Ju,Xu, Yun-He,Loh, Teck-Peng
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supporting information
p. 914 - 917
(2017/02/26)
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- Formation of: N -sulfonyl imines from iminoiodinanes by iodine-promoted, N-centered radical sulfonamidation of aldehydes
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A mild and operationally convenient formation of synthetically valuable N-sulfonyl imines from a range of aryl aldehydes by reaction with iminoiodinanes (PhINZ) and I2 has been developed. According to mechanistic experiments described within, the reaction is speculated to proceed through an unconventional light-promoted, N-centered radical (NCR) pathway involving a N,N-diiodosulfonamide reactive species. This method not only provides a new pathway toward the production of activated imines, but also serves as an example of a non-traditional means of carbonyl activation via an NCR species.
- Hopkins, Megan D.,Scott, Kristina A.,Demier, Brettany C.,Morgan, Heather R.,Macgruder, Jesse A.,Lamar, Angus A.
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p. 9209 - 9216
(2017/11/14)
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- Direct synthesis of N-sulfinyl- and N-sulfonylimines via copper/l-proline-catalyzed aerobic oxidative cascade reaction of alcohols with sulfinamides or sulfonamides
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An efficient one-pot synthetic method of N-sulfinyl- and N-sulfonylimines by the condensation of alcohols with sulfinamides or sulfonamides under mild and green conditions has been developed using a combination of CuI, l-proline and TEMPO. This system shows excellent functional group compatibility for a wide range of substrates and affords the corresponding products in good to excellent yields.
- Zhang, Guofu,Xu, Shengjun,Xie, Xiaoqiang,Ding, Chengrong,Shan, Shang
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p. 9431 - 9435
(2017/02/15)
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- Tunable titanocene lewis acid catalysts for selective friedel-crafts reaction of indoles and N-sulfonylaldimines
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A newc strategy to control the selective Friedel-Crafts reaction of indoles and imines under mild conditions was developed. Phenol derivatives were established as efficient ligands to finely tune the activity of titanocene dichloride. Cp2TiCl2 and phenol catalyzed the mono-Friedel-Crafts reaction of indoles and N-sulfonyl aldimines with good yields (91 %), whereas o-aminophenol significantly enhanced the activity of the titanocene catalyst and promoted the synthesis of bisindole with excellent yields (98 %). The new organometallic Lewis acid catalysts are air-tolerant, can be used with low catalyst loading (3 mmol-%) and are compatible with -NO2, -F, -Cl, -Br, and -OMe (30 examples with yields from good to excellent). The titanocene catalysts were fully characterized by NMR and HRMS analysis. The results suggest that Cp2TiCl(OC6H5) (I) and Cp2TiCl(OC6H4NH3+Cl-) (II) were catalytic species for the mono- and double-Friedel-Crafts reactions, respectively. Distinguished from single functional acid catalysts I, catalyst II showed a catalytic cooperative effect of two acid components, which led to a fine tuning of the reactivity as well as to the selectivity of the desired reaction pathways. A Ti-catalyzed, highly selective Friedel-Crafts reaction of indoles and imines has been developed. Cp2TiCl2 and phenol, with a single Lewis acid site, catalyzed the mono-Friedel-Crafts reaction of indoles and N-sulfonylaldimines, whereas o-aminophenol enhanced the acidity of titancene catalyst, enabling both Lewis and Bronsted acid sites to promote the synthesis of bisindole.
- Xiu, Wang,Zhenhua, Wang,Zhang, Guofang,Zhang, Weiqiang,Wu, Ya,Gao, Ziwei
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supporting information
p. 502 - 507
(2016/02/18)
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- Enantioselective Synthesis of α-Amino Phosphonates via Pd-Catalyzed Asymmetric Hydrogenation
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A highly enantioselective palladium-catalyzed hydrogenation of a series of linear and cyclic α-iminophosphonates has been achieved, providing efficient access to optically active α-aminophosphonates with up to 99% ee. (Chemical Equation Presented).
- Yan, Zhong,Wu, Bo,Gao, Xiang,Chen, Mu-Wang,Zhou, Yong-Gui
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supporting information
p. 692 - 695
(2016/03/01)
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- Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles
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Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.
- Yasukawa, Tomohiro,Kuremoto, Tatsuya,Miyamura, Hiroyuki,Kobayashi, Sh?
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supporting information
p. 2716 - 2718
(2016/06/15)
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- Aza-Morita-Baylis-Hillman reactions catalyzed by a cyclopropenylidene
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Catalysis using a bis(dialkylamino)cyclopropenylidene (BAC) has been developed, which relies on a formal umpolung activation of Michael acceptor pro-nucleophiles. Various aza-Morita-Baylis-Hillman reactions between aromatic, heteroaromatic, or aliphatic imines and acyclic or cyclic α,β-unsaturated ketones and carboxylic acid derivatives have been catalyzed by a BAC under mild conditions. Functionalities such as unprotected amino and hydroxy groups have been tolerated. The catalyst loading was decreased to 1 mol% without loss of activity. The BAC catalyst was shown to be substantially more active than a cyclic (alkyl)(amino) carbene (CAAC), N-heterocyclic carbenes (NHCs), and P- or N-centered Lewis bases.
- Lu, Xun,Schneider, Uwe
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supporting information
p. 12980 - 12983
(2016/11/09)
-
- Catalyst-controlled regiodivergent vinylogous aza-Morita–Baylis–Hillman reactions
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Regiodivergent vinylogous aza-Morita–Baylis–Hillman reactions of 3-vinylcyclopent-2-en-1-one 1 were developed in a catalyst-controlled manner. While treatment of 1 with N-tosylarylaldimines 2 in the presence of DABCO gave the α-adducts as the sole regiois
- Hyakutake, Ryuichi,Gondo, Naruhiro,Ueda, Yoshihiro,Yoshimura, Tomoyuki,Furuta, Takumi,Kawabata, Takeo
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supporting information
p. 1321 - 1324
(2018/03/29)
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- Metal-catalyzed formal amidation of alkenes under CO-free condition
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An effective procedure for synthesis of amides from alkenes and [Formula presented] via Pd and Fe catalysts under mild conditions is described. A series of benzamides containing various functional groups can be obtained in reasonable yield and the possible reaction pathway is proposed in this Letter.
- Zhang, Yuanyuan,Ye, Wenjing,Leng, Xue,He, Ying,Zhang, Hui,Xiao, Xiao
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supporting information
p. 4203 - 4206
(2016/08/24)
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- Synthesis of N-Sulfonyl Arylaldimines Developed by Retesting an Old Process
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By simply heating the mixture of an arylaldehyde and a sulfonylisocyanate in a solvent or in neat form under catalyst- and additive-free conditions, the desired N-sulfonylimine was produced with the release of carbon dioxide. The method is characterized b
- Huang, Dayun,Wang, Xuesong,Wang, Xingyong,Chen, Wenwen,Wang, Xinyan,Hu, Yuefei
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supporting information
p. 604 - 607
(2016/02/18)
-
- Selective Synthesis of Tripyrranes, Tetrapyrranes, and Corroles
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A new, catalytic, and general methodology was developed for the direct synthesis of unsymmetrical AB-type tripyrranes by reaction of dipyrromethanesulfonamides with pyrrole. Key structure dipyrromethanesulfonamides were synthesized by the addition of meso
- Aydin, Gokcen,Temelli, Baris,Unaleroglu, Canan
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p. 7583 - 7593
(2016/01/25)
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- A Mannich/cyclization cascade process for the asymmetric synthesis of spirocyclic thioimidazolidineoxindoles
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An asymmetric cascade Mannich/cyclization reaction between 3-isothiocyanato oxindoles and sulfimides using a commercially available organocatalyst has been developed. A wide range of structurally diverse spiro[imidazolidine-4,3′-oxindole] derivatives were
- Cai, Hao,Zhou, Yu,Zhang, Dong,Xu, Jinyi,Liu, Hong
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supporting information
p. 14771 - 14774
(2015/01/09)
-
- Synthesis of di-, tri-, and tetrasubstituted pyridines from (phenylthio)carboxylic acids and 2-[aryl(tosylimino)methyl]acrylates
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An isothiourea-catalyzed Michael addition-lactamization followed by the sulfide oxidation-elimination/N- to O-sulfonyl transfer sequence for the formation of 2,3,5- and 2,3-substituted pyridine 6-tosylates from (phenylthio)acetic acids and α,β-unsaturated
- Stark, Daniel G.,O'Riordan, Timothy J. C.,Smith, Andrew D.
-
supporting information
p. 6496 - 6499
(2015/02/05)
-
- Enantioselective continuous-flow production of 3-indolylmethanamines mediated by an immobilized phosphoric acid catalyst
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A polystyrene-supported 1,1'-bi-2-naphthol derived phosphoric acid has been synthesized and applied in the enantioselective Friedel-Crafts reaction of indoles and sulfonylimines. The immobilized catalyst was highly active and selective, and gave rise to a
- Osorio-Planes, Laura,Rodriguez-Escrich, Carles,Pericas, Miquel A.
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supporting information
p. 2367 - 2372
(2014/03/21)
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- Dehydrogenation and oxidative coupling of alcohol and amines catalyzed by organosilicon-supported TiO2@PMHSIPN
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The catalytic dehydrogenation and tandem transformation of aromatic alcohols, including oxidative coupling of alcohols and amines, were achieved successfully using a catalytic amount of organosilicon-supported titania (TiO2@PMHSIPN), which enables the efficient synthesis of aromatic aldehydes, imines, and benzimidazoles in good to excellent yields. This journal is the Partner Organisations 2014.
- Wang, Hu,Zhang, Jin,Cui, Yu-Ming,Yang, Ke-Fang,Zheng, Zhan-Jiang,Xu, Li-Wen
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p. 34681 - 34686
(2014/11/08)
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- Heterobimetallic Ir-Sn catalysis: Aza-Friedel-Crafts reaction of N-sulfonyl aldimines
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The heterobimetallic complex [Ir(COD)(SnCl3)Cl(μ-Cl)] 2 catalyzes the aza-Friedel-Crafts reaction of 1,3,5- trimethoxybenzene, as well as substituted indoles with N-sulfonyl aldimines leading to the formation of diarylamines and triarylmethanes in good yields. The symmetrical triarylmethanes were also obtained from diarylamines and suitable nucleophiles via simultaneous cleavage of sp3 C-N bond and elimination of 1,3,5-trimethoxybenzene.
- Chatterjee, Paresh Nath,Maity, Arnab Kumar,Mohapatra, Swapna Sarita,Roy, Sujit
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supporting information
p. 2816 - 2826
(2013/04/10)
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- One-pot preparation of homopropargylic N-sulfonylamines catalyzed by zinc powder
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A new one-pot method for synthesis of homopropargylic N-sulfonylamines from aldehydes catalyzed by zinc powder is described. The procedure is lauded by its simplicity, good yields, and adaptability to a wide variety of aldehydes.
- Wu, Chao,Huang, Wangyong,He, Weimin,Xiang, Jiannan
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supporting information
p. 1233 - 1234
(2013/10/22)
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- Rh(III)-catalyzed olefination of N-sulfonyl imines: Synthesis of ortho -olefinated benzaldehydes
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Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes has been achieved for the synthesis of ortho-olefinated benaldehydes. This reaction proceeds via a chelation assisted C-H olefination/in situ hydrolysis process.
- Zhang, Tao,Wu, Lamei,Li, Xingwei
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supporting information
p. 6294 - 6297
(2014/01/17)
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- Hydrocyanation of sulfonylimines using potassium hexacyanoferrate(II) as an eco-friendly cyanide source
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An efficient and eco-friendly method for hydrocyanation of sulfonylimines via one-pot two-step procedure using potassium hexacyanoferrate(II) as a cyanide source, benzoyl chloride as a promoter, and potassium carbonate as a base is described. This protocol has the features of using nontoxic, nonvolatile and inexpensive cyanide source, high yield, and simple work-up procedure.
- Li, Zheng,Li, Rongzhi,Zheng, Huanhuan,Wen, Fei,Li, Hongbo,Yin, Junjun,Yang, Jingya
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p. 1739 - 1743
(2014/01/06)
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- Synthesis of N-sulfonylimines using CeCl3 under neutral conditions
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An efficient and environmentally benign method for the synthesis of N-sulfonylimines is reported. Condensation of aryl sulfonamides with different aromatic aldehydes and ketones gave N-sulfonylimines in good to excellent yields in the presence of 10 mol% CeCl3 as catalyst. This method can be used with both aldehydes and ketones.
- Zhu, Xun,Wei, Yunyang
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experimental part
p. 363 - 364
(2012/09/22)
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- Chiral diphosphane- and NHC-containing ruthenium catalysts for the catalytic asymmetric arylation of aldimines with organoboron reagents
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For the first time, we report the application of [RuCl2(η 6-p-cymene)]2 in the arylation of N-activated aldimines with boronic acids and its derivatives to afford chiral amines, which are important intermediates in the syntheses of key bioactive compounds. The behavior of the chiral ligands, the imine substrates, and the organoboron reagents were studied. Very good enantioselectivities were obtained. A new method is presented for the synthesis of chiral substituted amines by employing Ru catalysts along with known chiral phosphane ligands and a new NHC-type chiral ligand. Organoboron reagents were applied as the aryl transfer agents. High enantioselectivities were achieved with this new method, and some mechanistic insights are provided.
- Marques, Carolina S.,Burke, Anthony J.
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supporting information; experimental part
p. 4232 - 4239
(2012/09/22)
-
- Nucleophilic addition of regioselectively lithiated indoline with aldimines for the syntheses of 2- and 7-indolinyl methanamine derivatives
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Indolines bearing different N-protecting groups (N-Tbf and N-Boc) were deprotonated regioselectively at C-2 (sp3 hybridized ortho-H) and C-7 (sp2 hybridized para-H) of the indoline ring, respectively. The generated organolithium intermediates reacted with aldimines to give the desired products in good yields with excellent anti-diastereoselectivities (>99:1). The produced N-Ts-(1-Tbf-indolin-2-yl)methanamine was facilely transformed to a fused heterocyclic compound.
- Cheng, Liang,Liu, Li,Li, Chuan,Jia, Han,Wang, Dong,Chen, Yong-Jun
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supporting information; experimental part
p. 4004 - 4007
(2012/09/05)
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- Rh-catalyzed C-C cleavage of benzyl/allylic alcohols to produce benzyl/allylic amines or other alcohols by nucleophilic addition of intermediate rhodacycles to aldehydes and imines
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We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl-directed Rh-catalyzed C-C bond cleavage of secondary alcohols and subsequent addition to C=X (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of C-C bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in-depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron-rich alcohols and electron-deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the C-C bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The C-C cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the C-C cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of C-C cleavage/nucleophilic addition and C-C cleavage/protonation/C-H activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)-C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the "group transplant", this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.
- Zhang, Xi-Sha,Li, Yang,Li, Hu,Chen, Kang,Lei, Zhi-Quan,Shi, Zhang-Jie
-
supporting information
p. 16214 - 16225
(2013/02/21)
-
- α-Aryl-substituted allenamides in an imino-nazarov cyclization cascade catalyzed by Au(I)
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An imino-Nazarov cyclization using α-aryl-substituted allenamides is described. This gold(I)-catalyzed cascade is efficient and regioselective in constructing a diverse array of synthetically useful aromatic-ring fused cyclopentenamides. The success in this transformation represents a solution to the challenge in establishing an imino-Nazarov cyclization process.
- Ma, Zhi-Xiong,He, Shuzhong,Song, Wangze,Hsung, Richard P.
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supporting information
p. 5736 - 5739
(2013/01/15)
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- Ruthenium- and sulfonamide-catalyzed cyclization between N-sulfonyl imines and alkynes
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Ruthenium(II)-catalyzed redox-neutral annulative coupling of N-sulfonyl imines with alkynes has been achieved for the synthesis of indenamines, where a sulfonamide cocatalyst is necessary.
- Zhao, Peng,Wang, Fen,Han, Keli,Li, Xingwei
-
supporting information
p. 5506 - 5509,4
(2020/10/15)
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- Efficient and convenient preparation of N-tosylimines catalyzed by indium trichloride
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A new method for preparation of N-tosylimines by InCl3-mediated condensation of aldehydes with p-toluenesulfonamide in refluxing benzene is reported. The procedure is lauded by its simplicity, mild reaction conditions, excellent yields and adap
- Deng, Gui Sheng,Zou, Jing Yuan,Sun, Teng Fei
-
scheme or table
p. 511 - 514
(2012/01/05)
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- Synthesis of 2-amino-1,3-dienes by chromium-catalyzed addition of silylated propargyl bromides to imines
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(Silyl)methylallenic amines were synthesized by the chromium-catalyzed addition of (4-bromobutynyl)trimethylsilane to tosyl imines. Regioisomeric mixtures of the desired allene and the corresponding alkyne were obtained. Allenic imines were then treated w
- Durán-Galván, María,Connell, Brian T.
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experimental part
p. 7901 - 7908
(2011/11/07)
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- Dinuclear zinc catalyzed asymmetric Friedel-Crafts amidoalkylation of indoles with aryl aldimines
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The asymmetric Friedel-Crafts amidoalkylation of indoles with aryl aldimines could be efficiently catalyzed by Trost's bis-ProPhenol dinuclear zinc complexes to attain 3-indolyl methanamine derivatives in good to excellent yields (85-98%) with moderate to high enantiomeric ratios (from 70:30 up to 95:5 er). Remarkably, this approach provides efficient access to enantiomerically enriched 3-indolyl methanamines, which avoids the formation of the undesirable bis- and tris(indolyl)methanes (BIMs and TIMs) byproduct.
- Wang, Bei-Lei,Li, Nai-Kai,Zhang, Jin-Xin,Liu, Guo-Gui,Liu, Teng,Shen, Qi,Wang, Xing-Wang
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supporting information; experimental part
p. 2614 - 2617
(2011/05/08)
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- Dimethylsulfoxide-promoted Strecker reaction of N-tosylaldimines with cyanoformate
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A metal-free method for performing the Strecker reaction of N-tosylaldimines with ethyl cyanoformate in dimethylsulf-oxide (DMSO) has been developed. Various types of N-tosyl-aldimines undergo the cyanation to provide the N-protected -amino nitriles. This
- Kadam, Santosh T.,Thirupathi, Ponnaboina,Kim, Sung Soo
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scheme or table
p. 919 - 923
(2011/05/07)
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- Asymmetric Mannich reaction of imines derived from aliphatic and aromatic aldehydes catalyzed by diarylprolinol silyl ether
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Anti Mannich, try this! A direct asymmetric Mannich reaction catalyzed by a diarylprolinol silyl ether was developed to afford the anti-Mannich product with excellent enantioselectivity. Imines derived from both aliphatic and aromatic aldehydes were successfully used to obtain the synthetically important β-amino aldehydes (see scheme; Ts=tosyl). The reaction can also be performed in the presence of water. Copyright
- Urushima, Tatsuya,Ishikawa, Hayato,Hayashi, Yujiro
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supporting information; experimental part
p. 8273 - 8276
(2011/09/12)
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- Organic hydrogen phosphites and hydrogen phosphates catalyzed Friedel-Crafts amidoalkylation of indoles with aryl aldimines
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A highly efficient and selective Friedel-Crafts amidoalkylation reaction of indoles with N-Ts aryl aldimines has been developed utilizing dimethyl hydrogen phosphite or diphenyl hydrogen phosphate as the organocatalysts, providing a facile and cost-effect
- Wang, Bei-Lei,Zhang, Jin-Xin,Li, Nai-Kai,Liu, Guo-Gui,Shen, Qi,Wang, Xing-Wang
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supporting information; experimental part
p. 4671 - 4674
(2011/10/01)
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- Asymmetric aza-friedel-crafts reaction of 2-naphthol with tosylimines catalyzed by a dinuclear zinc complex
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The first asymmetric aza-Friedel-Crafts reaction of 2-naphthol with tosylimines was developed via a dinuclear zinc catalyst (up to 98% ee). It provided a new method for the asymmetric synthesis of Betti base derivatives.
- Niu, Liang-Feng,Xin, Yang-Chun,Wang, Ren-Lin,Jiang, Fan,Xu, Peng-Fei,Hui, Xin-Ping
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supporting information; experimental part
p. 765 - 768
(2010/06/14)
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- Indium triflate-catalyzed allylation reactions of N-sulfonyl aldimines or N-alkoxycarbonylamino p-tolylsulfones with allyltrimethylsilane: Synthesis of protected homoallylic amines
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Indium triflate-catalyzed allylation reactions of N-sulfonyl aldimines or N-alkoxyloxycarbonylamino p-tolylsulfone with allyltrimethylsilane have been successfully developed to produce protected homoallylic amines.
- Thirupathi, Ponnaboina,Kim, Sung Soo
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scheme or table
p. 8623 - 8628
(2010/11/18)
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- Base-promoted selective β-fragmentation of homoallylamines
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A selective β-fragmentation of homoallylamines with the combination of iodobenzene diacetate, iodine, and sodium acetate is reported. The desired carbon-carbon bond cleavage proceeded via a radical β-scission pathway under mild conditions with good functional group tolerance.
- Li, Weixun,Gan, Jianhong,Fan, Renhua
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experimental part
p. 4275 - 4277
(2010/09/07)
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- The first example of saccharin-lithium bromide catalysis: Direct synthesis of N-tosylimines from alcohols
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The first procedure to access N-tosylimines directly from alcohols under mild and neutral conditions is reported. The protocol involves saccharin-lithium bromide-catalyzed oxidation of alcohols to aldehydes/ketones with chloramine-T followed by their condensation with the in situ generated oxidation by-product p-toluenesulfonamide in the same reaction vessel to afford N-tosylimines in 40-90% overall yields. The present work opens up a new and efficient synthetic route to N-tosyimines directly from alcohols in a one-pot procedure.
- Patel, Rajesh,Srivastava, Vishnu P.,Yadav, La Dhar S.
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experimental part
p. 1610 - 1614
(2010/09/05)
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