- Chiral Br?nsted-Acid-Catalyzed Asymmetric Oxidation of Sulfenamide by Using H2O2: A Versatile Access to Sulfinamide and Sulfoxide with High Enantioselectivity
-
Herein, we describe an example of catalytic asymmetric synthesis of sulfinamides. Aromatic sulfenamides were chosen as useful substrates, because of the indispensable N-H bond, which could form an efficient hydrogen bond with chiral phosphoric acid. Hsub
- Ma, Long-Jun,Chen, Shu-Sen,Li, Guang-Xun,Zhu, Jin,Wang, Qi-Wei,Tang, Zhuo
-
p. 1525 - 1530
(2019/02/01)
-
- Stereoselective synthesis of isoindolinones and tert-butyl sulfoxides
-
A reaction of Grignard reagents with an optically pure N-sulfinylimine derived from methyl 2-formylbenzoate yields enantioenriched isoindolinones and tert-butyl sulfoxides. The products are formed by the addition of the nucleophile to N-sulfinylimine followed by cyclization to form N-tert-butylsulfinylisoindolinone, which readily undergoes substitution with a second equivalent of Grignard reagent. The reaction can be carried out in dichloromethane at room temperature or at elevated temperatures without any loss of stereoselectivity. The use of nucleophiles other than Grignard reagents has also been investigated.
- Kaw?cki, Robert,Stańczyk, Wojciech,Jaglińska, Agnieszka
-
p. 578 - 584
(2017/12/28)
-
- Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions
-
The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.
- Xia, Qingchun,Li, Zijian,Tan, Chunxia,Liu, Yan,Gong, Wei,Cui, Yong
-
supporting information
p. 8259 - 8266
(2017/06/28)
-
- Atropo-diastereoselective coupling of aryllithiums and arynes — variations around the chiral auxiliary
-
The atropo-selective coupling of in situ generated arynes and aryllithiums bearing various chiral auxiliaries ortho to lithium (tert-butylsulfoxide, para-tolylsulfoxide, tartrate-derived chiral diethers and oxazolines) is described. Chiral oxazolines showed the best results in terms of yields of coupling products. Different reaction parameters like the nature of the aryne precursor, the oxazoline, the alkyllithium base or the solvent revealed to be crucial for obtaining good yields and for diastereoselection.
- Augros, David,Yalcouye, Boubacar,Berthelot-Bréhier, Ana?s,Chessé, Matthieu,Choppin, Sabine,Panossian, Armen,Leroux, Frédéric R.
-
p. 5208 - 5220
(2016/08/02)
-
- Diastereoconvergent synthesis of trans -5-hydroxy-6-substituted-2- piperidinones by addition-cyclization-deprotection process
-
A diastereoselective one-pot approach to access trans-5-hydroxy-6- substituted-2-piperidinones by an addition-cyclization-deprotection process has been developed, in which the stereogenic center at the C-6 position was solely controlled by α-OTBS group. The utility of this transformation is demonstrated by the asymmetric synthesis of the enantiomer of (-)-CP-99,994.
- Si, Chang-Mei,Huang, Wei,Du, Zhen-Ting,Wei, Bang-Guo,Lin, Guo-Qiang
-
supporting information
p. 4328 - 4331
(2014/09/30)
-
- Enantioselective access to benzannulated spiroketals using a chiral sulfoxide auxiliary
-
This article describes our efforts to develop an asymmetric synthesis of bisbenzannulated spiroketals using a chiral sulfoxide auxiliary. Our primary focus was on the synthesis of the 3H-spiro[benzofuran-2,2′-chroman] ring system, the spirocyclic core of the rubromycin family. Our strategy employed the use of lithium-halogen exchange on a racemic bromospiroketal in order to attach a chiral sulfoxide, thus producing two diastereomers. The diastereomers were separable, enabling isolation of each spiroketal enantiomer. Subsequent cleavage of the sulfoxide group from each diastereomer yielded the respective parent spiroketal in high enantiopurity.
- Aitken, Harry R. M.,Furkert, Daniel P.,Hubert, Jonathan G.,Wood, James M.,Brimble, Margaret A.
-
p. 5147 - 5155
(2013/08/15)
-
- PROCESS FOR THE ASYMMETRIC OXIDATION OF ORGANIC COMPOUNDS WITH PEROXIDES IN THE PRESENCE OF A CHIRAL ACID CATALYST
-
The present invention relates to a process for the asymmetric oxidation of nucleophilic organic compounds, particularly metal-free, with peroxide compounds in the presence of a chiral Bronsted acid catalyst. In one detail, the present invention relates to a process for enantioselective sulfoxidation of thiocompounds with peroxide compounds in the presence of a chiral imidodiphosphate catalyst. In another detail, the present invention relates to a process for enantioselective sulfoxidation of thiocompounds with peroxide compounds in the presence of a chiral phosphoric acid catalyst.
- -
-
Page/Page column 26
(2013/07/25)
-
- BINOL derived C2-symmetric bis-sulfinates as efficient sulfinyl transfer agents in the synthesis of tert-butyl sulfoxides
-
The reaction of novel C2-symmetric bis-sulfinate esters derived from (R)-BINOL with Grignard reagents affords tert-butyl sulfoxides in ee up to 97%. The desired enantiomer can be generated at will by the proper selection of BINOL.
- Gaggero,Albanese
-
scheme or table
p. 7129 - 7132
(2012/09/05)
-
- Desymmetrization of prochiral diaryl sulfoxides by an asymmetric sulfoxide-magnesium exchange
-
The first desymmetrizations of prochiral diaryl sulfoxides 1 by an asymmetric sulfoxide-magnesium exchange reaction are reported. The respective substrate (1), iPr2Mg, and the dilithium salt of (S)-BINOL (which was prepared in situ) provided (S)-configured aryl isopropyl sulfoxides 2 in up to 91 % yield and with up to 91 % ee. (S)-BINOL was re-isolable in 98 % yield. Copyright
- Hampel, Thomas,Ruppenthal, Simon,Saelinger, Daniel,Brueckner, Reinhard
-
p. 3136 - 3140
(2012/05/20)
-
- Tert-Butanesulfinylthioether ligands: Synthesis and application in palladium-catalyzed asymmetric allylic alkylation
-
A class of novel chiral SO-S-type bidentate ligands based on the tert-butylsulfinyl moiety as the sole chiral source were designed and synthesized through a simple and efficient pathway. These ligands are effective catalyst precursors for the palladium-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate and moderate to good stereoselectivities (up to 84% ee) were obtained.
- Liu, Jibing,Chen, Guihua,Xing, Junwei,Liao, Jian
-
experimental part
p. 575 - 579
(2011/06/21)
-
- Planar chiral flavinium salts - Prospective catalysts for enantioselective sulfoxidation reactions
-
A novel planar chiral flavinium salt, 3-benzyl-5-ethyl-10-(8- phenylnaphthalen-1-yl)isoalloxazinium perchlorate (2b), which bears a phenyl cap that covers one side of the isoalloxazinium skeleton plane, has been prepared as a potential catalyst for the enantioselective H2O2 oxidation of sulfides. The rate of H2O2 oxidation of sulfides in the presence of racemic 2b is comparable to that of the reaction catalysed by 5-ethyl-3,10-dimethylisoalloxazinium perchlorate, which indicates that the bulky shielding substituent does not influence the catalytic activity of the flavinium unit. The turnover frequency for the oxidation of thioanisole with hydrogen peroxide with 2b is 870 h-1. The enantiomerically pure salts (+)-2b and (-)-2b were prepared from the pure enantiomers (+)-3b and (-)-3b of 3-benzyl-10-(8-phenylnaphthalen-1-yl)isoalloxazine (3b) obtained by HPLC separation of racemic 3b on a chiral stationary phase. The enantiomerically pure salts (+)-2b and (-)-2b catalyse the H2O2 oxidation of para-substituted thioanisoles with enantiomeric excesses of 34-44%. The highest enantioselectivity (54% ee) was observed in the oxidation of methyl naphthyl sulfide.
- Jurok, Radek,Cibulka, Radek,Dvorakova, Hana,Hampl, Frantisek,Hodacova, Jana
-
experimental part
p. 5217 - 5224
(2010/11/02)
-
- Synthesis of new sulfoxide-containing diselenides and unexpected cyclization reactions to 2,3-dihydro-1,4-benzoselenothiine 1-oxides
-
New chiral sulfoxide-containing diselenides were prepared and their corresponding selenium, electrophiles were used for the stereoselective functionalization of alkenes. The influence of solvents and different nucleophiles on the outcome of the selenenylation reaction was studied. Besides the successful selenenylation reactions, one selenium electrophile showed an unexpected reactivity in forming a six-membered heterocyclic system, upon reaction with, alkenes. A mechanism for the formation of these 2,3-dihydro-1,4-benzoselenothiine 1-oxides is proposed. 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
- Freudendahl, Diana M.,Iwaoka, Michio,Wirth, Thomas
-
scheme or table
p. 3934 - 3944
(2010/09/05)
-
- Aryl tert-butyl sulfoxide-promoted highly enantioselective addition of allyltrichlorosilane to aldehydes
-
A series of enantiomerically pure mono- and bis-aryl tert-butyl sulfoxides were synthesised to promote the enantioselective allylation of aldehydes with allyltrichlorosilane. Moderate to good yields and modest to high enantioselectivities were achieved. The absence of nonlinear effect, spacer effect, promoter loading and concentration effect indicate that only one molecule of aryl tert-butyl sulfoxide is involved in the stereodetermining step.
- Wang, Peng,Chen, Junmin,Cun, Linfeng,Deng, Jingen,Zhu, Jin,Liao, Jian
-
experimental part
p. 3741 - 3747
(2009/10/24)
-
- Enantioselective inclusion of chiral alkyl aryl sulfoxides in a supramolecular helical channel consisting of an enantiopure 1,2-amino alcohol and an achiral carboxylic acid
-
The enantioselective clathrate formation of alkyl aryl sulfoxides 4 was achieved with dissymmetric one-dimensional helical channels created in two-component hosts consisting of (1R,2S)-2-amino-1,2-diphenylethanol 1 and an achiral carboxylic acid, p-tert-butylbenzoic acid 2, or 2-anthraquinonecarboxylic acid 3. X-ray crystallographic analyses showed that the host framework (1R,2S)-1·3 in the single crystal of a clathrate with methyl p-methylphenyl sulfoxide 4n [(1R,2S)-1·3·4n (single)] maintained a supramolecular helical array as those of the solvent-included single crystals (1R,2S)-1·3·EtOH(single) and (1R,2S)-1·3·H2O·THF(single), while the guest 4n molecules were highly disordered. Moreover, the X-ray powder diffraction pattern of (1R,2S)-1·3·4n(clathrate) obtained through the clathrate formation demonstrated that the molecular arrangements of (1R,2S)-1, 3, and 4n were not the same as those which appeared in (1R,2S)-1·3·4n(single); the channel was enlarged. These results are consistently explained by assuming the dynamic motion of the framework (1R,2S)-1·3 to achieve widely applicable clathrate formation.
- Kobayashi, Yuka,Soetrisno,Kodama, Koichi,Saigo, Kazuhiko
-
p. 295 - 301
(2008/09/19)
-
- Catalytic asymmetric diethylzinc addition to diphenylphosphionyl imines using chiral tert-butanesulfinylphosphine ligands
-
A class of novel chiral tert-butanesulfinylphosphine ligands were designed and synthesized by a concise two-step route with high yields. High activities and enantioselectivities (up to 94% ee) were achieved when using them in catalytic asymmetric diethylz
- Chen, Junmin,Li, Dong,Ma, Haifeng,Cun, Linfeng,Zhu, Jin,Deng, Jingen,Liao, Jian
-
supporting information; experimental part
p. 6921 - 6923
(2009/04/07)
-
- ortho-metalation of enantiopure aromatic sulfoxides and stereocontrolled addition to imines
-
Enantiopure aromatic (phenyl, naphthyl) and heteroaromatic (pyridyl, quinolyl, diazinyl) sulfoxides have been synthesized by reaction of (5)-tert-butyl tert-butanethiosulfinate with aryl- or heteroaryllithium derivatives. The ortho-directed metalation of
- Le Fur, Nicolas,Mojovic, Ljubica,Ple, Nelly,Turck, Alain,Reboul, Vincent,Metzner, Patrick
-
p. 2609 - 2616
(2007/10/03)
-
- Catalytic enantioselective sulfinyl transfer using cinchona alkaloid catalysts
-
(Chemical Equation Presented) Practical reaction conditions for the catalytic enantioselective synthesis of sulfinate esters are reported. Commercially available cinchona alkaloids were found to be superior catalysts for the sulfinyl transfer reaction of tert-butanesulfinyl chloride and a variety of benzyl alcohols. Sulfinyl transfer with 2,4,6-trichlorobenzyl alcohol and 10 mol % of the commercially available, inexpensive catalyst quinidine provided the pure sulfinate ester product in 92% isolated yield and with 90% ee.
- Peltier, Hillary M.,Evans, Jared W.,Ellman, Jonathan A.
-
p. 1733 - 1736
(2007/10/03)
-
- A method of manufacturing an amine stereoisomerically
-
This invention provides intermediates useful in a method of preparing amine stereoisomers. It also provides a method of preparing sulfoxide and sulfinylamine stereoisomers using certain of the intermediates.
- -
-
Page/Page column 57-58
(2010/02/12)
-
- Practical and highly stereoselective technology for preparation of enantiopure sulfoxides and sulfinamides utilizing activated and functionally differentiated N-sulfonyl-1,2,3-oxathiazolidine-2-oxide derivatives
-
A simple, general, and practical technology to prepare enantiopure 1,2,3-oxathiazolidine-2-oxide derivatives using chiral aryl N-sulfonyl aminoalcohol derivatives and thionyl chloride is reported. The versatility of these novel chiral building blocks (MIOO and TMPOO), was exemplified by the expedient production of a variety of unique chiral sulfoxides and valuable chiral sulfinamides in excellent yields and enantiopurities.
- Han, Zhengxu,Krishnamurthy, Dhileepkumar,Grover, Paul,Fang, Q. Kevin,Su, Xiping,Wilkinson, H. Scott,Lu, Zhi-Hui,Magiera, Daniel,Senanayake, Chris H.
-
p. 6386 - 6408
(2007/10/03)
-
- New general sulfinylating process for asymmetric synthesis of enantiopure sulfinates and sulfoxides
-
(Chemical Equation Presented) A general process for the efficient synthesis of sulfinyl transfer agents has been developed using cinchona alkaloids quinine and quinidine as chiral auxiliaries. The importance of these new and unique sulfinyl transfer agent
- Lu, Bruce Z.,Jin, Fuqiang,Zhang, Yongda,Wu, Xinhe,Wald, Stephen A.,Senanayake, Chris H.
-
p. 1465 - 1468
(2007/10/03)
-
- Catalytic enantioselective synthesis of sulfinate esters through the dynamic Resolution of tert-butanesulfinyl chloride
-
Development of a new synthetic route to obtain enantiomerically enriched tert-butanesulfinate esters in excellent yields through catalytic enantioselective sulfinyl transfer is described. As little as 0.5 mol % of chiral amine catalysts was used to couple racemic tert-butanesulfinyl chloride with arylmethyl alcohols to provide sulfinate esters in near quantitative yields and with enantiomeric excesses up to 81%. The method represents the first example of the catalytic dynamic resolution of sulfinyl derivatives. Copyright
- Evans, Jared W.,Fierman, Matthew B.,Miller, Scott J.,Ellman, Jonathan A.
-
p. 8134 - 8135
(2007/10/03)
-
- Diastereomeric sulfinates derived from (L)-N-methylephedrine: Synthesis, applications and rearrangements
-
The reaction of sulfinyl chlorides with (L)-N-methylephedrine alone or in the presence of tertiary amines was found to produce diastereomeric sulfinates with diastereomeric purities up to 90%. The diastereomeric ratio is strongly influenced by the nature
- Drabowicz, Jozef,Bujnicki, Bogdan,Biscarini, Paolo,Mikolajczyk, Marian
-
p. 3177 - 3187
(2007/10/03)
-
- Sulfoxides of High Enantiopurity from Bacterial Dioxygenase-catalysed Oxidation
-
Selected strains of the bacterium Pseudomonas putida (previously shown to effect dioxygenase-catalysed asymmetric cis-dihydroxylation of alkenes) have been found to yield chiral sulfoxides from the corresponding sulfides with a strong preference for the (R)- or (S)-configurations but without evidence of sulfone formation; similar results obtained using an Escherichia coli clone (pKST11, containing the Tod C1 C2 B and A genes encoding toluene dioxygenase from P. putida NCIMB 11767) are again consistent with a stereoselective dioxygenase-catalysed sulfoxidation.
- Allen, Christopher C. R.,Boyd, Derek R.,Dalton, Howard,Sharma, Narain D.,Haughey, Simon A.,et al.
-
p. 119 - 120
(2007/10/02)
-
- A General Route to Enantiomerically Pure Sulfoxides from a Chiral Sulfite
-
Enantiomerically pure cyclic chiral sulfite (S)-7 (trans stereochemistry) has been easily obtained in two steps from (S)-ethyl lactate.This compound was found to react cleanly with many organometallics to give crystalline sulfinates with high regioselecti
- Rebiere, F.,Samuel, O.,Ricard, L.,Kagan, H.B.
-
p. 5991 - 5999
(2007/10/02)
-
- Asymmetric Oxidation of Alkyl Aryl Sulfides in Crystalline Cyclodextrin Complexes
-
Alkyl aryl sulfides were enantioselectively oxidized in the crystalline cyclodextrin (CD) complexes under various conditions.The oxidation of alkyl phenyl sulfoxides in the β-cyclodextrin (β-CD) complexes resulted in higher chiral induction than that in t
- Sakuraba, Hidetake,Natori, Kazuhiro,Tanaka, Yoshio
-
p. 4124 - 4129
(2007/10/02)
-
- Enantioselective oxidation of sulphides to sulphoxides in the presence of bovine serum albumin
-
In situ generated dioxiranes oxidize a series of prochiral sulphides to the corresponding sulphoxides with enantiomeric excess (e.e.) up to 89%, when bovine serum albumin (BSA) is used as chiral auxiliary. The degree of enantioselectivity, as well as yield and reaction times, depend upon the nature of the dioxirane. These are compared with enantioselectivities attainable for the same transformations by using peroxomonosulfate alone, i.e. in the absence of ketone. In the oxidation of prochiral keto sulphides (wherein the carbonyl functionality serves as precursor of dioxirane) with peroxomonosulfate, optically active keto sulphoxides are isolated in satisfactory chemical and optical yield (up to e.e. 84%).
- Colonna,Gaggero,Leone,Pasta
-
p. 8385 - 8398
(2007/10/02)
-
- AN EFFICIENT ROUTE TO CHIRAL t-BUTYL SULFOXIDES
-
The cyclic sulfite 2 of (S)-1,1-diphenyl-propane-1,2-diol 1 gave chiral sulfinates 3 or 4 with high regio- and stereoselectivities, by reaction with various organometallics.The chiral sulfinates were then transformed in almost quantitative yields into ena
- Rebiere, F.,Kagan, H.B.
-
p. 3659 - 3662
(2007/10/02)
-
- ENANTIOSELECTIVE OXIDATION OF SULPHIDES BY DIOXIRANES IN THE PRESENCE OF BOVINE SERUM ALBUMIN
-
Oxidation of sulphides by in situ generated dioxiranes in buffered (pH 7.5) aqueous solutions, using bovine serum albumin (BSA) as a chiral auxiliary, affords the corresponding sulphoxides in up to 89percent enantiomeric excess (e.e.).
- Colonna, Stefano,Gaggero, Nicoletta
-
p. 6233 - 6236
(2007/10/02)
-
- ORGANOSULPHUR COMPOUNDS-LXIX OPTICALLY ACTIVE SULPHINATES: A NEW TYPE OF ENANTIOSELECTIVE ASYMMETRIC SYNTHESIS AND KINETIC RESOLUTION
-
Optically active sulphinates with the sulphur atom as a sole centre of chirality are prepared by two methods.The first involves the reaction of symmetrical sulphites with tert-butylmagnesium chloride in the presence of optically active aminoalcohols.This new asymmetric, enantioselective synthesis affords t-butylsulphinates with 40-70percent enantiomeric excess values.The second approach is based on a new type of kinetic resolution taking place when racemic sulphinates are reacted with tert-butylmagnesium chloride complexed by optically active alkaloid bases.Both the recovered sulphinates and sulphoxides formed in this reaction show moderate optical purities.
- Drabowicz, Jozef,Legedz, Slawomir,Mikolajczik, Marian
-
p. 5243 - 5252
(2007/10/02)
-
- Chemistry of Oxaziridines. 3. Asymmetric Oxidation of Organosulfur Compounds Using Chiral 2-Sulfonyloxaziridines
-
Chiral 2-sulfonyloxaziridines, 9-12, afford the best enantioselectivity of any chiral oxidizing reagent for the asymmetric oxidation of sulfides and disulfides to sulfoxides and thiosulfinates, respectively, 5-8 times better than chiral peracids.For asymmetric oxidations using 9-12, the configuration of the oxaziridine three-membered ring was shown to control the configuration of the product, which could be predicted using a chiral recognition mechanism (Figure 2).The increased asymmetric bias exhibited by chiral 2-sulfonyloxaziridines was attrbuted to the fact that the active-site oxygen was incorporated into a rigid chiral environment.The group size difference (GSD) effect in both the oxaziridine and substrate play important roles in determining the absolute configuration of the product and the magnitude of the asymmetric bias.As the GSD increases the enantioselectivity increases.
- Davis, Franklin A.,Jenkins, Robert H.,Awad, Sami B.,Stringer, Orum D.,Watson, William H.,Galloy, Jean
-
p. 5412 - 5418
(2007/10/02)
-