- Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C-H Functionalization Enabled by Chiral Carboxylic Acid
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Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining C-H cleavage step remains undeveloped. Here we describe a Ru(II)-catalyzed enantioselective C-H activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using a novel class of chiral binaphthyl monocarboxylic acids as chiral ligands, which can be easily and modularly prepared from 1,1′-binaphthyl-2,2′-dicarboxylic acid. A broad range of sulfur-stereogenic sulfoximines were prepared in high yields with excellent enantioselectivities (up to 99% yield and 99% ee) via desymmetrization, kinetic resolution, and parallel kinetic resolution. Furthermore, the resolution products can be easily transformed to chiral sulfoxides and key intermediates for kinase inhibitors.
- Zhou, Tao,Qian, Pu-Fan,Li, Jun-Yi,Zhou, Yi-Bo,Li, Hao-Chen,Chen, Hao-Yu,Shi, Bing-Feng
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supporting information
p. 6810 - 6816
(2021/05/29)
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- Chiral Dibenzopentalene-Based Conjugated Nanohoops through Stereoselective Synthesis
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Conjugated nanohoops allow to investigate the effect of radial conjugation and bending on the involved π-systems. They can possess unexpected optoelectronic properties and their radially oriented π-system makes them attractive for host–guest chemistry. Be
- Hermann, Mathias,Wassy, Daniel,Kohn, Julia,Seitz, Philipp,Betschart, Martin U.,Grimme, Stefan,Esser, Birgit
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p. 10680 - 10689
(2021/04/02)
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- Sulfur-Based Chiral Iodoarenes: An Underexplored Class of Chiral Hypervalent Iodine Reagents
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Chiral hypervalent iodine reagents are active players in modern stereoselective organic synthesis. Structurally diverse chiral hypervalent iodine reagents have been synthesised and extensively studied, but hypervalent iodine reagents containing chiral sul
- Alharbi, Haifa,Elsherbini, Mohamed,Karam, Fatemah,Osi, Arnaud,Wirth, Thomas
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- General Method for the Asymmetric Synthesis of N-H Sulfoximines via C-S Bond Formation
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A versatile method for the synthesis of enantioenriched N-H sulfoximines is reported. The approach stems from the organomagnesium-mediated ring opening of novel cyclic sulfonimidate templates. The reactions proceed in high yield and with excellent stereofidelity with alkyl, aryl, and heteroaryl Grignard reagents. The chiral auxiliary is readily removed from the resultant sulfoximines via an unusual oxidative debenzylation protocol that utilizes molecular oxygen as the terminal oxidant. This provides a general strategy for the synthesis of highly enantioenriched N-H sulfoximines.
- Argent, Stephen P.,Lewis, William,Mendon?a Matos, Priscilla,Moore, Jonathan c.,Stockman, Robert A.
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- Efficient Kinetic Resolution of Sulfur-Stereogenic Sulfoximines by Exploiting CpXRhIII-Catalyzed C?H Functionalization
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Chiral sulfoximines with stereogenic sulfur atoms are promising motifs in drug discovery. We report an efficient method to access chiral sulfoximines through a C?H functionalization based kinetic resolution. A rhodium(III) complex equipped with a chiral Cpx ligand selectively participates in conjunction with phthaloyl phenylalanine in the C?H activation of just one of the two sulfoximine enantiomers. The intermediate reacts with various diazo compounds, providing access to chiral 1,2-benzothiazines with synthetically valuable substitution patterns. Both sulfoximines and 1,2-benzothiazines were obtained in high yields and excellent enantioselectivity, with s-values of up to 200. The utility of the method is illustrated by the synthesis of the key intermediates of two pharmacologically relevant kinase inhibitors.
- Brauns, Marcus,Cramer, Nicolai
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p. 8902 - 8906
(2019/06/04)
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- Iron(II)-Catalyzed Direct Synthesis of NH Sulfoximines from Sulfoxides
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Free NH-sulfoximines were directly prepared from sulfoxides through iron catalysis by applying a readily available, shelf-stable hydroxylamine triflic acid salt. No additional oxidant is needed, and the substrate scope is broad, including a range of heter
- Yu, Hao,Li, Zhen,Bolm, Carsten
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supporting information
p. 324 - 327
(2017/12/15)
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- Enantiopure sulfoximines-catalyzed 1, 4-additions to 2-en-ketone
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An efficient chiral catalyst procedure for the preparation of β-chiral ketone via the 1, 4-additions reaction of 2-en-ketone has been developed using enantiopure sulfoximines modified with functional groups as ligands. The carefully design and synthesized
- Zhao, Hongwei,Han, Hui,Yang, Hengquan,wang, Li
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p. 210 - 213
(2018/06/26)
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- Organocatalytic Kinetic Resolution of Sulfoximines
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An efficient kinetic resolution of sulfoximines with enals was realized using chiral N-heterocyclic carbene (NHC) catalysts. The stereoselective amidation proceeds without additional acyl transfer agent. Both enantiomers of the sulfoximines can be obtaine
- Dong, Shunxi,Frings, Marcus,Cheng, Hanchao,Wen, Jian,Zhang, Duo,Raabe, Gerhard,Bolm, Carsten
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supporting information
p. 2166 - 2169
(2016/03/05)
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- Transfer of Electrophilic NH Using Convenient Sources of Ammonia: Direct Synthesis of NH Sulfoximines from Sulfoxides
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A new system for NH transfer is developed for the preparation of sulfoximines, which are emerging as valuable motifs for drug discovery. The protocol employs readily available sources of nitrogen without the requirement for either preactivation or for met
- Zenzola, Marina,Doran, Robert,Degennaro, Leonardo,Luisi, Renzo,Bull, James A.
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supporting information
p. 7203 - 7207
(2016/07/06)
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- Asymmetric synthesis of γ-lactones through reaction of sulfoxonium ylides, aldehydes, and ketenes
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A method for the enantioselective synthesis of γ-lactones through the reaction of enantioenriched sulfoxonium ylides, aldehydes, and ketenes was developed. Enantioenriched (98% ee) aminosulfoxonium ylide was subjected to reaction with a variety of aldehydes (both aromatic and aliphatic) and disubstituted ketenes, leading to the formation of α,β-substituted γ-lactones in moderate to very good diastereoselectivity (dr up to 95:5) and with enantiomeric excesses of up to 79% ee. Best levels of enantioselectivity were observed in the reactions of enantioenriched aminosulfoxonium ylide with isobutyraldehyde and various alkylarylketenes.
- Peraino, Nicholas J.,Ho, Han-Jen,Mondal, Mukulesh,Kerrigan, Nessan J.
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p. 4260 - 4263
(2014/07/22)
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- Rhodium-catalyzed stereoselective amination of thioethers with n-mesyloxycarbamates: DMAP and Bis(DMAP)CH2Cl2 as key additives
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A stereoselective Rh-catalyzed intermolecular amination of thioethers using a readily available chiral N-mesyloxycarbamate to produce sulfilimines in excellent yields and diastereomeric ratio is described. A catalytic mixture of 4-dimethylaminopyridine (DMAP) and bis(DMAP)CH2Cl2 proved pivotal in achieving high selectivity. The X-ray crystal structure of the (DMAP)2·[Rh2{(S)-nttl}4] complex was obtained and mechanistic studies suggested a RhII-RhIII complex as the catalytically active species.
- Lebel, Hélène,Piras, Henri,Bartholoméüs, Johan
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supporting information
p. 7300 - 7304
(2014/07/21)
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- Enantioselective nitrene transfer to sulfides catalyzed by a chiral iron complex
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Iron works: Enantioselective nitrene transfer to sulfide was accomplished by a chiral iron(III)/PyBOX catalyst (see scheme). Various sulfimides were thus obtained in high enantioselectivities and yields. Applications of this protocol to the syntheses of enantioenriched sulfoximines and an epoxide were also demonstrated. Copyright
- Wang, Jun,Frings, Marcus,Bolm, Carsten
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p. 8661 - 8665
(2013/09/12)
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- Sulfoximines: A reusable directing group for chemo-and regioselective ortho C-H oxidation of arenes
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Sulfoximines direct: A new protocol for the chemo-and regioselective ortho C-H acetoxylation of arenes in N-benzoylated sulfoximines is reported. The sulfoximine directing group is easily detached from the C-H oxidation product through acid-promoted hydrolysis, isolated, and reused (see scheme). The meta-substituted phenols are synthesized following this strategy and the stereointegrity of the sulfoximine is preserved in this transformation. C(sp3)-H acetoxylation of the methyl group is also demonstrated.
- Yadav, M. Ramu,Rit, Raja K.,Sahoo, Akhila K.
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p. 5541 - 5545
(2012/06/01)
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- Synthesis of chiral α-(N-sulfoximido) phosphines, phosphine oxides, and phosphonates through hydrophosphination and hydrophosphorylation of N-vinyl sulfoximines
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The reaction of N-vinyl sulfoximines with HPPh2, HP(O)Ph 2, and HP(O)(OMe)2 gave the corresponding α-(N-sulfoximido) phosphines, phosphine oxides, and phosphonates, respectively, with high regioselectivity in high yield. The N-vinyl sulfoximines showed an enamine-like regioselectivity in hydrophosphination and hydrophosphorylation (Pudovik reaction). While the acid-catalyzed hydrolysis of a cyclic N-vinyl sulfoximine gave the corresponding NH-sulfoximine and cyclohexanone, its hydroboration/oxidation afforded the corresponding N-(β-hydroxycyclohexenyl) sulfoximine. The structure of an α-(N-sulfoximido) phosphine was determined by X-ray crystal structure analysis. Georg Thieme Verlag Stuttgart.
- Hetzer, Ralf Helmut,Gais, Hans-Joachim,Raabe, Gerhard
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p. 1126 - 1132
(2008/12/22)
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- Iron-catalyzed imination of sulfoxides and sulfides
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The Fe(III)-catalyzed imination of sulfoxides and sulfides with sulfonylamides in the presence of iodinanes has been investigated. The best results were obtained when Fe(acac)3 was used as a catalyst in combination with iodosylbenzene, providin
- Mancheno, Olga Garcia,Bolm, Carsten
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p. 2349 - 2352
(2007/10/03)
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- Silver-catalyzed imination of sulfoxides and sulfides
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(Chemical Equation Presented) Silver salts in the presence of a chelating ligand efficiently catalyze the stereospecific imination of sulfoxides and sulfides with sulfonylamides and Phl(OAc)2 to afford sulfoximines and sulfilimines, respectivel
- Gae, Young Cho,Bolm, Carsten
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p. 4983 - 4985
(2007/10/03)
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- Synthesis of (S)-N-(diphenylphosphinyl)-S-methyl-S-phenyl sulfoximide: A new ligand for asymmetric catalysis
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The synthesis of (S)-N-(diphenylphosphinyl)-S-methyl-S-phenyl sulfoximide is reported. Preliminary investigations into the use of this novel sulfoximide as a ligand for asymmetric conjugate addition reactions are also described.
- Kinahan, Taryn C.,Tye, Heather
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p. 1255 - 1257
(2007/10/03)
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- The search for benchrotrenes and ferrocenes containing a chiral sulfoximido group: Preparation and structural properties
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Syntheses of chiral benchrotrene and ferrocene complexes bearing N- protected sulfonimidoyl moieties are reported. They are obtained by metal- catalyzed imination reactions starting from enantiopure sulfoxides. An X-ray structure analysis was carried out for one of the novel complexes confirming the stereospecificity of the imination process.
- Bolm,Muniz,Aguilar,Kesselgruber,Raabe
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p. 1251 - 1260
(2007/10/03)
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- The preparation of N-tert-butyloxycarbonyl-(Boc-)protected sulfoximines and sulfimines by an iron(II)-mediated nitrene transfer from BocN3 to sulfoxides and sulfides
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The imidation of sulfides and sulfoxides to the corresponding sulfimides and sulfoximides was carried out with N-tert-butyloxycarbonyl azide (BocN3) in the presence of FeCl2. Sulfoxides 1 reacted at room temperature in CH2
- Bach, Thorsten,Koerber, Christina
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p. 1033 - 1039
(2007/10/03)
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- An efficient resolution of (±)-S-methyl-S-phenylsulfoximine with (±)-10-camphorsulfonic acid by the method of half-quantities
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Racemic S-methyl-S-phenylsulfoximine (±)-1 can be resolved with only 0.6 equivalents of (+)-camphorsulfonic acid by avoiding any recrystallization to give (+)-1 of ≤99% ee in 80% yield and (-)-1 of 97-99% ee in 74% yield. This procedure, which is based on
- Brandt, Jochen,Gais, Hans-Joachim
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p. 909 - 912
(2007/10/03)
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