- Asymmetric Friedel-Crafts addition of indoles to N-sulfonyl aldimines: A simple approach to optically active 3-indolyl-methanamine derivatives
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The enantioselective copper(II)-catalyzed Friedel-Crafts addition of indoles to N-sulfonyl aldimines was developed using chiral bisoxazoline as ligands, and high enantioselectivities (up to 96% ee) were achieved.
- Jia, Yi-Xia,Xie, Jian-Hua,Duan, Hai-Feng,Wang, Li-Xin,Zhou, Qi-Lin
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- TfOH-catalyzed formal [3+2] cycloaddition of N-tosylaziridine dicarboxylates and nitriles: Synthesis of tetrafunctionalized 2-imidazolines
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We developed an efficient method for synthesis of tetrafunctionalized 2-imidazolines using TfOH-catalyzed formal [3+2] cycloaddition of N-tosylaziridine dicarboxylates and nitriles. This is the first report of C–N bond cleavage of N-tosylaziridine dicarboxylates catalyzed by Br?nsted acid and the reaction worked well over wide scope of substrates in good to excellent yields under mild conditions. The method has the potential to be applied to pharmaceutical design and synthesis of tetrafunctionalized 2-imidazolines.
- Zuo, Qinglu,Shi, Zhichao,Zhan, Feng,Wang, Zhe,Lin, Jin-Shun,Jiang, Yuyang
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supporting information
(2020/01/13)
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- The Generation of Difluoroketenimine and Its Application in the Synthesis of α,α-Difluoro-β-amino Amides
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Fluorine-containing β-amino acids and their derivatives have attracted significant attention due to their importance in life sciences. Herein the previously unknown difluoroketenimine, the analogue of the elusive difluoroketene, has been generated by the
- Zhang, Rui,Zhang, Zhikun,Zhou, Qi,Yu, Lefei,Wang, Jianbo
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supporting information
p. 5744 - 5748
(2019/03/28)
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- Synthesis of Benzyl Amines via Copper-Catalyzed Enantioselective Aza-Friedel-Crafts Addition of Phenols to N -Sulfonyl Aldimines
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A new copper-catalyzed enantioselective aza-Freidel-Crafts reaction between phenols and N-sulfonyl aldimines that provides chiral secondary benzylamines in good to excellent yields and excellent enantioselectivities (up to 99% ee) is disclosed. In particular, excellent scope with alkylimines was observed for the first time. The synthetic utility of the products was demonstrated in the first enantioselective synthesis of a dual orexin receptor antagonist, a compound that contains an amine-bearing stereocenter adjacent to a bis-ortho-functionalized arene.
- Shikora, Jonathan M.,Chemler, Sherry R.
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supporting information
p. 2133 - 2137
(2018/04/30)
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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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- Probing the Diastereoselectivity of Staudinger Reactions Catalyzed by N-Heterocyclic Carbenes
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The reaction of ethylphenylketene with 1,3-dimesitylimidazol-2-ylidene (IMes) or 1,3-dimesitylimidazolin-2-ylidene (SIMes) afforded the corresponding azolium enolates in high yields. The two zwitterions were fully characterized by various analytical techn
- Hans, Morgan,Wouters, Johan,Demonceau, Albert,Delaude, Lionel
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supporting information
p. 10870 - 10877
(2015/07/20)
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- Catalytic asymmetric synthesis of dihydroquinazolinones from imines and 2-aminobenzamides
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An unprecedented catalytic asymmetric synthesis of aminal-containing heterocyclic compounds has been developed from imines and tethered nitrogen/nitrogen nucleophiles. In the presence of 10mol% of a commercially available chiral phosphoric acid, a range of aromatic, α,β- unsaturated, and aliphatic imines react with 2-aminobenzamides to give dihydroquinazolinones in good to excellent yields and ee. The enantioselectivity is significantly affected by the imine N-substituent through non-bonding interactions with the chiral phosphoric acid and the 2-aminobenzamide. Copyright
- Cheng, Dao-Juan,Tian, Yu,Tian, Shi-Kai
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supporting information; experimental part
p. 995 - 999
(2012/06/01)
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- Rhodium-catalyzed synthesis of branched amines by direct addition of benzamides to imines
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Rhodium-catalyzed addition of benzamide C-H bonds to a range of aromatic N-sulfonyl aldimines has been developed and proceeds with high functional group compatibility. The synthetic utility of the resulting branched amine products has also been demonstrated by the preparation of isoindoline and isoindolinone frameworks.
- Hesp, Kevin D.,Bergman, Robert G.,Ellman, Jonathan A.
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supporting information; experimental part
p. 2304 - 2307
(2012/06/30)
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- Rhodium(III)-catalyzed arylation of Boc-imines via C-H bond functionalization
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The first rhodium-catalyzed arylation of imines proceeding via C-H bond functionalization is reported. Use of a non-coordinating halide abstractor is important to obtain reactivity. Aryl-branched N-Boc-amines are formed, and a wide range of functionality is compatible with the reaction.
- Tsai, Andy S.,Tauchert, Michael E.,Bergman, Robert G.,Ellman, Jonathan A.
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supporting information; experimental part
p. 1248 - 1250
(2011/04/16)
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- One-pot nitro-Mannich/hydroamination cascades for the direct synthesis of 2,5-disubstituted pyrroles using base and gold catalysis
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An efficient, easy to perform, one-pot reaction cascade for the synthesis of 2,5-disubstituted pyrroles from p-toluenesulfonyl protected imines and 4-nitrobut-1-yne under a combination of base and gold(iii) catalysis is reported.
- Barber, David M.,Sanganee, Hitesh,Dixon, Darren J.
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supporting information; body text
p. 4379 - 4381
(2011/06/17)
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- N-Nosyl oxaziridines as terminal oxidants in copper(II)-catalyzed olefin oxyaminations
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We report that N-4-nosyl-3-phenyloxaziridine is an effective terminal oxidant for copper(II)-catalyzed oxyamination recently developed in our labs. This oxaziridine can be prepared on multi-gram scale and is easily purified by recrystallization. The products of oxyamination using this oxaziridine bear protecting groups that can be readily removed in high yields under mild conditions.
- Deporter, Sandra M.,Jacobsen, Ashley C.,Partridge, Katherine M.,Williamson, Kevin S.,Yoon, Tehshik P.
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scheme or table
p. 5223 - 5225
(2010/11/03)
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- A highly tunable stereoselective olefination of semistabilized triphenylphosphonium ylides with N -Sulfonyl imines
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The Wittig reaction involving direct olefination of triphenylphosphonium ylides (Ph3PCHR) with aldehydes is arguably the most often used method for alkene synthesis, but in general it yields mixtures of Z- and E-alkenes for semistabilized triphenylphosphonium ylides (R = aryl or vinyl). We have developed a simple and efficient protocol to improve the stereoselectivity significantly by replacing the aldehydes used in the Wittig reaction with N-sulfonyl imines, which possess distinct electronic and steric properties relative to aldehydes. A broad range of aromatic, α,β-unsaturated, and aliphatic imines bearing appropriate N-sulfonyl groups smoothly undergo olefination reaction with various benzylidenetriphenylphosphoranes or allylidenetriphenylphosphoranes under mild reaction conditions to afford an array of both Z- and E-isomers of conjugated alkenes in good to excellent yields and with greater than 99:1 stereoselectivity. Moreover, this tunable protocol has been successfully applied to the highly stereoselective synthesis of two anticancer agents, DMU-212 and its Z-isomer.
- Dong, De-Jun,Li, Hai-Hua,Tian, Shi-Kai
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supporting information; experimental part
p. 5018 - 5020
(2010/06/13)
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- A 4-hydroxypyrrolidine-catalyzed mannich reaction of aldehydes: Control of anti-selectivity by hydrogen bonding assisted by bronsted acids
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An anti-selective Mannich reaction of aldehydes with N-sulfonyl imines has been developed by using a 4-hydroxypyrrolidine in combination with an external Bronsted acid. The catalyst design is based on three elements: the ct-substituent of the pyrrolidine, the 4-hydroxy group, and the Bronsted acid, the combination of which is essential for high chemical and stereochemical efficiency. The reaction works with aromatic aldehydederived imines, which have rarely been employed in previously reported enamine-based anti-Mannich reactions. Additionally, both N-tosyl and N-nosyl imines can be successfully used and the Mannich adducts can be easily reduced or oxidized, and after N-deprotection the corresponding ss-amino acids and ss-amino alcohols can be obtained with good yields. The results also show that this ternary catalytic system may be practical in other enamine-based reactions.
- Gomez-Bengoa, Enrique,Maestro, Miguel,Mielgo, Antonia,Otazo, Itziar,Palomo, Claudio,Velilla, Irene
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supporting information; experimental part
p. 5333 - 5342
(2010/10/03)
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- A novel synthesis of 1-nosyl 3,3-dichloro-β-lactams and derivatives
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(Chemical Equation Presented) We report herein an efficient and simple route to synthesize 1-nosyl 3,3-dichloro-β-lactams using a Staudinger reaction between N-nosyl imines and dichloroketene. The resulting dichloroazetidines were opened to afford highly functionalized building blocks.
- Tato, Francisco,Reboul, Vincent,Metzner, Patrick
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supporting information; experimental part
p. 7837 - 7840
(2009/04/03)
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- Cycloadditions of N-sulfonyl nitrones generated by Lewis acid catalyzed rearrangement of oxaziridines
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We have developed cycloaddition reactions of novel, electron-deficient N-nosyl nitrones that arise from the titanium(IV)-catalyzed rearrangement of the corresponding N-nosyl oxaziridines. A diverse range of styrenes and oxaziridines react smoothly in this
- Partridge, Katherine M.,Anzovino, Mary E.,Yoon, Tehshik P.
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p. 2920 - 2921
(2008/10/09)
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- Small-molecule inhibitors of protein geranylgeranyltransferase type I
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Small molecules that inhibit the geranylgeranylation of K-Ras4B and RhoA by protein geranylgeranyltransferase type I (GGTase-I) were identified from chemical genetic screens of heterocycles synthesized through phosphine catalysis of allenes. To further improve the efficacy of the GGTase-I inhibitors (GGTIs), 4288 related compounds bearing core dihydropyrrole/pyrrolidine and tetrahydropyridine/piperidine scaffolds were synthesized on SynPhase lanterns in a split-pool manner through phosphine-catalyzed [3 + 2] and [4 + 2] annulations of resin-bound allenoates. Testing of the 4288 analogues resulted in several GGTIs exhibiting submicromolar IC50 values. Because proteins such as Ras and Rho GTPases are implicated in oncogenesis and metastasis, these GGTIs might ultimately lead to the development of novel antitumor therapeutics. Copyright
- Castellano, Sabrina,Fiji, Hannah D. G.,Kinderman, Sape S.,Watanabe, Masaru,De Leon, Pablo,Tamanoi, Fuyuhiko,Kwon, Ohyun
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p. 5843 - 5845
(2008/03/14)
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- A copper(II)-catalyzed aza-friedel-crafts reaction of N-(2-Pyridyl)sulfonyl aldimines: Synthesis of unsymmetrical diaryl amines and triaryl methanes
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(Chemical Equation Presented) The choice of the (2-pyridyl)sulfonyl moiety as an N-protecting group and Cu(OTf)2/(±)-binap as catalyst system lead to a highly efficient aza-Friedel-Crafts reaction of electron-rich arenes (Ar2-H) and heteroarenes with N-sulfonyl imines. This protocol is also amenable to the synthesis of unsymmetrical triaryl methanes through a second electrophilic aromatic substitution with a different electron-rich arene (Ar3-H; see scheme).
- Esquivias, Jorge,Arrayas, Ramon Gomez,Carretero, Juan C.
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p. 629 - 633
(2007/10/03)
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- Highly enantioselective aza-Baylis-Hillman reactions catalyzed by chiral thiourea derivatives
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We report the discovery of asymmetric aza-Baylis-Hillman (ABH) reactions of N-p-nitrobenzenesulfonylimines with methyl acrylate catalyzed by chiral thiourea derivatives. A series of aromatic imines was found to undergo coupling with methyl acrylate with u
- Raheem, Izzat T.,Jacobsen, Eric N.
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p. 1701 - 1708
(2007/10/03)
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- C2-symmetric bicyclo[3.3.1]nonadiene as a chiral ligand for rhodium-catalyzed asymmetric arylation of N-(4-nitrobenzenesulfonyl)arylimines
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(Chemical Equation Presented) Asymmetric synthesis of diarylmethylamines with high enantioselectivity (95-99percent ee) was realized by use of a new C 2-symmetric diene ligand, (1R,5R)-2,6-diphenylbicyclo[3.3.1]nona-2,6- diene (Ph-bnd*), for th
- Otomaru, Yusuke,Tokunaga, Norihito,Shintani, Ryo,Hayashi, Tamio
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p. 307 - 310
(2007/10/03)
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- Imino ene reaction catalyzed by Ytterbium(III) Triflate and TMSCl or TMSOTf
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A novel combined system of Yb(OTf)3 with TMSCl or TMSOTf catalyzed an imino ene reaction. The reaction of N-tosylbenzaldimine (1) with α-methylstyrene (2) proceeded smoothly to give homoallylic amine 3 in the presence of a catalytic amount of Y
- Yamanaka, Masamichi,Nishida, Atsushi,Nakagawa, Masako
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p. 3112 - 3120
(2007/10/03)
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- A Novel [3+2] Cycloaddition Approach to Nitrogen Heterocycles via Phosphine-Catalyzed Reactions of 2,3-Butadienoates or 2-Butynoates and Dimethyl Acetylenedicarboxylate with Imines: A Convenient Synthesis of Pentabromopseudilin
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The reactivity of a new three carbon synthon, generated in situ from the reaction of 2,3-butadienoates 2-butynoates with an appropriate phosphine as the catalyst, toward the electron-deficient imines is described. Triphenylphosphine-catalyzed reaction of methyl 2,3-butadienoate with N-sulfonylimines gave the single [3+2] cycloadduct in excellent yield; tributylphosphine-catalyzed reaction of methyl 2,3-butadienoate or 2-butynoate with N-tosylimines afforded the corresponding [3+2] cycloadduct as the major product along with a small amount of the three components adduct. Aliphatic N-tosylimines gave moderate yield for this reaction. In addition, a new phosphine-catalyzed cyclization reaction of dimethyl acetylenedicarboxylate with N-tosylimines is also described. A reaction mechanism is proposed. Further elaborations of the cycloaddition products and the synthesis of pentabromopseudilin using this method are exemplified.
- Xu, Zhenrong,Lu, Xiyan
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p. 5031 - 5041
(2007/10/03)
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- Rhodium(II)-Catalyzed CH Insertions with imino>phenyl-λ3-iodane
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The catalyzed decomposition of imino>phenyl-λ3-iodane (NsN=IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents.Scope and limitations of the reaction were investigated.Yields of up to 84percent were achieved in the most favorable cases.Yields were enhanced by electron-releasing substituents and decreased by steric hindrance.Aziridination competed with allylic insertion with olefinic substrates.The insertion reaction proceeded with retention of configuration.With chiral RhII catalysts, a modest asymmetric induction was observed.A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.
- Naegeli, Ivo,Baud, Corine,Bernardinelli, Gerald,Jacquier, Yvan,Moran, Mary,Mueller, Paul
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p. 1087 - 1105
(2007/10/03)
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- Rhodium(II)-catalyzed aziridinations and ch insertions with [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane
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The [Rh2(OAc)4]-catalyzed decomposition of NsN=IPh {[N-(p-nitrobenzenesulfonyl)imino]phenyliodinane} in the presence of olefins affords aziridines in yields of up to 85%. The aziridination of cis-hex-2-ene and cis-β-methylstyrene is stereospecific, but, cis-stilbene affords a 3:1 mixture of cis- and trans-aziridines in low yield. With chiral Rh(II) catalysts, optically active aziridines are formed having enantiomeric excesses of up to 73%. The NsN-IPh-[Rh2(OAc)4] system is also efficient for the allylic amination of olefins and for insertion into CH bonds, activated by phenyl or oxygen substituents.
- Mueller, Paul,Baud, Corine,Jacquier, Yvan,Moran, Mary,Naegeli, Ivo
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p. 341 - 347
(2007/10/03)
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- HAMMETT INVESTIGATION OF IODIDE-ION-INDUCED DEOXYGENATIVE REDUCTION OF 2-ARYL'SULPHONYL-3 ARYLOXAZIRIDINES IN METHANOL-WATER (50percent v/v)
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The Hammett substituent dependence of the iodide ion induced deoxygenation of 2-aryl'sulphonyl-3-aryloxaziridines, in aqu. methanol suggests that the reaction proceeds by nucleophilic attack on oxygen with concomitant O-N bond breakage.
- Knipe, A. C.,McAuley, I. E.,Khandelwal, Y.,Kansal, V. K.
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p. 1411 - 1414
(2007/10/02)
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- Chemistry of Oxaziridines. 1. Synthesis and Structure of 2-Arenesulfonyl-3-aryloxaziridines. A New Class of Oxaziridines
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A new class of oxaziridine derivatives, 2-arenesulfonyl-3-aryloxaziridines (2), is prepared by m-CPBA oxidation of sulfonimines (RSO2N=CHAr).These compounds are the first stable examples of this ring system to have a substituent other than carbon attached to nitrogen and are characterized by a highly electrophilic oxaziridine oxygen atom.These oxaziridines have the E configuration as determined by X-ray crystallography.The presence of the powerful electron-attracting sulfonyl group attached to nitrogen apparently has little effect on the structure of the oxaziridine three-membered ring.Of more significance are the observations that the nitrogen lone pair in 2 is opposite to one of the sulfonyl oxygens and that the long S-N bond length implies little if any conjugative interaction between sulfur and nitrogen.Attempts to prepare oxaziridines via oxidation of sulfonimines, 5, derived from acetophenone gave imidoyl ether 14, a novel Baeyer-Villiger oxidation product of a C-N double bond.
- Davis, Franklin A.,Lamendola, Joseph,Nadir, Upender,Kluger, Edward W.,Sedergran, Thomas C.,et al.
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p. 2000 - 2005
(2007/10/02)
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