- Ni/Photoredox-Catalyzed Enantioselective Cross-Electrophile Coupling of Styrene Oxides with Aryl Iodides
-
A Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides is reported. This reaction affords access to enantioenriched 2,2-diarylalcohols from racemic epoxides via a stereoconvergent mechanism. Multivariate linear regression (MVLR) analysis with 29 bioxazoline (BiOx) and biimidazoline (BiIm) ligands revealed that enantioselectivity correlates with electronic properties of the ligands, with more electron-donating ligands affording higher ee's. Experimental and computational mechanistic studies were conducted, lending support to the hypothesis that reductive elimination is enantiodetermining and the electronic character of the ligands influences the enantioselectivity by altering the position of the transition state structure along the reaction coordinate. This study demonstrates the benefits of utilizing statistical modeling as a platform for mechanistic understanding and provides new insight into an emerging class of chiral ligands for stereoconvergent Ni and Ni/photoredox cross-coupling.
- Lau, Sii Hong,Borden, Meredith A.,Steiman, Talia J.,Wang, Lucy S.,Parasram, Marvin,Doyle, Abigail G.
-
supporting information
p. 15873 - 15881
(2021/10/12)
-
- Visible-Light-Induced Charge Transfer Enables Csp3-H Functionalization of Glycine Derivatives: Access to 1,3-Oxazolidines
-
A photoredox catalyst free, visible-light-induced aerobic oxidative [2 + 3] cycloaddition reaction between glycine derivatives and styrene oxides has been disclosed that provides an efficient approach for the rapid synthesis of 1,3-oxazolidines under mild
- Li, Ying,Xie, Zhixiang,Yang, Xiaorong,Zhang, Yuan,Zhu, Yin
-
supporting information
p. 1638 - 1643
(2020/03/13)
-
- Use of allylzinc halide as a source of halide: Differential addition of nucleophiles to Ts-aziridines and aldehydes under similar reaction conditions
-
We have observed that the allylic zinc halide under identical reaction conditions acts in different modes for different electrophiles. For Ts-aziridines the halide part of the allylic halide has been introduced as a nucleophile and for the carbonyl compou
- Chatterjee, Rana,Samanta, Satyajit,Mukherjee, Anindita,Santra, Sougata,Zyryanov, Grigory V.,Majee, Adinath
-
supporting information
p. 276 - 283
(2019/01/04)
-
- Palladium-Catalyzed Intermolecular Heck-Type Reaction of Epoxides
-
The palladium-catalyzed intermolecular Heck-type reaction of both cyclic and acyclic epoxides is reported with tolerance of typical polar groups and acidic protons. Suitable alkenes include styrenes, conjugate dienes, and some electron-deficient olefins. In reactions of aliphatic terminal epoxides, ring opening occurs selectively at terminal positions, and stereocenters of epoxides are fully retained. Mechanistic studies provide evidence for in situ conversion of epoxides to β-halohydrins, generation of alkyl radicals, and radical addition to alkenes as key steps. Cyclovoltammetric determination of reduction potentials suggests that during activation of alkyl iodides by palladium(0) complexes, inner-sphere halogen abstraction is more likely than outer-sphere single electron transfer.
- Teng, Shenghan,Tessensohn, Malcolm E.,Webster, Richard D.,Zhou, Jianrong Steve
-
p. 7439 - 7444
(2018/07/15)
-
- Intermolecular Tandem Addition/Esterification Reaction of Alkenes with Malonates Leading to γ-Lactones Mediated by Molecular Iodine under Visible Light Irradiation
-
The iodine-mediated intermolecular C?C bond-forming/esterification reaction of various alkenes including α-olefins with malonates under irradiation using a compact fluorescent lamp has been developed to synthesize γ-lactones in moderate to excellent yield
- Maejima, Saki,Yamaguchi, Eiji,Itoh, Akichika
-
supporting information
p. 3883 - 3887
(2017/09/18)
-
- 1,3,2,4-diazadiphosphetidine-based phosphazane oligomers as source of P(III) atom economy reagents: Conversion of epoxides to vic -haloalcohols, vic -dihalides, and alkenes in the presence of halogen sources
-
1,3,2,4-Diazadiphosphetidines (P1-P3), as easily prepared, stable, and heterogeneous P(III) compounds, were used for the efficient conversion of epoxides to vic-halohydrins, vic-dihalides, or alkenes in the presence of different halogen sources in CH3CN. Of these phosphazanes, P3 is most suitable and contains 4 phosphorous atoms with the advantage of having greater atom economy and its phosphorus oxide byproduct can be easily separated from the reaction mixture by simple filtration. The nitrogen atoms in this molecule can also act as acid scavengers in the reaction.
- Iranpoor, Nasser,Firouzabadi, Habib,Etemadidavan, Elham
-
p. 1165 - 1173
(2014/10/16)
-
- An improved protocol for regioselective ring-opening of sulfonyl aziridines with iodine promoted by PPh3
-
A new route to synthesize β-iodo amines from sulfonyl aziridines and iodine was developed in the presence of PPh3. This ring-opening reaction was an efficient and simple process to give β-iodo amines in excellent yields with high chemoselectivi
- Zhang, Jinfeng,Meng, Lingguo,Li, Chuntao,Xiao, Guoyuan
-
p. 1508 - 1512
(2014/01/06)
-
- H2TPP organocatalysis in mild and highly regioselective ring opening of epoxides to halo alcohols by means of halogen elements
-
We found that elemental iodine and bromine are converted to trihalide nucleophiles (triiodine and tribromide anion, respectively) in the presence of catalytic amounts of meso-tetraphenylporphyrins (H2TPP). Therefore a highly regioselective method for the synthesis of β-haloalcohols through direct ring opening of epoxides with elemental iodine and bromine in the presence of H2TPPs as new catalysts is described. At room temperature a series of epoxide derivatives were converted into the corresponding halohydrins resulting from an attack of trihalide species anion atoms at the less substituted carbon atom. This method occurs under neutral and mild conditions with high yields in various aprotic solvents, even when sensitive functional groups are present.
- Torabi, Parviz,Azizian, Javad,Zomorodbakhsh, Shahab
-
scheme or table
p. 5508 - 5519
(2012/08/28)
-
- A one-pot regioselective synthetic route to vinyl sulfones from terminal epoxides in aqueous media
-
A highly efficient LiBr catalysed regioselective synthesis of vinyl sulfones from readily available terminal epoxides and sodium sulfinates in a one-pot procedure using water as a reaction medium is reported. The protocol is adorned with several attributes of green chemistry like recycling of the catalyst, atom-economy and an aqueous medium.
- Chawla, Ruchi,Kapoor, Ritu,Singh, Atul K.,Yadav, Lal Dhar S.
-
experimental part
p. 1308 - 1313
(2012/06/01)
-
- Direct reaction of aryl iodides with activated aluminium powder and reactions of the derived aryl sesquiiodides
-
High temperature (110-120 °C) direct reaction of ArI (Ar = Ph, 1-C 10H7, 3-Tol) with aluminium powder in the presence of HgCl2 (1 mol%) or liquid gallium metal (10mol%) leads to quantitative conversion to the aryl sesquiiodides Al2Ar3I3. The latter, highly Lewis acidic, compounds are effective in opening of cyclic ethers and direct ester to amide conversions. Georg Thieme Verlag Stuttgart.
- Tang, Xiaoping,Rawson, Daniel,Woodward, Simon
-
scheme or table
p. 636 - 638
(2010/09/18)
-
- An efficient and convenient protocol for highly regioselective cleavage of terminal epoxides to β-Halohydrins
-
An efficient and facile strategy for the cleavage of terminal epoxides to β-halohydrins using active magnesium halides is described. The conversion proceeds smoothly at room temperature with high regioselectivity and good yields even when sensitive functional groups are present. Georg Thieme Verlag Stuttgart.
- Wang, Tao,Ji, Wen-Hao,Xu, Zhong-Yu,Zeng, Bu-Bing
-
experimental part
p. 1511 - 1513
(2009/10/23)
-
- Silphos [PCl3-n (SiO2)n]: A heterogeneous phosphine reagent for the regioselective synthesis of vic-haloalcohols
-
Silphos as a silica-based phosphine [PCl3-n (SiO 2)n] provides a practical method for the conversion of epoxides to vic-haloalcohols in the presence of molecular bromine, iodine, or N-halosuccinimides (NXS, X = Cl, Br, I) in CH3CN or under solvent-free conditions at r.t. The simple filtration of heterogeneous Silphos oxide from the reaction mixture affords the pure vic-haloalcohols with excellent yields. Copyright Taylor & Francis Group, LLC.
- Iranpoor, Nasser,Firouzabadi, Habib,Jamalian, Arezu
-
p. 2615 - 2621
(2007/10/03)
-
- Regioselective synthesis of vic-halo alcohols and symmetrical or unsymmetrical vic-dihalides from epoxides using triphenylphosphine -N-halo imides
-
A simple, novel, and highly regioselective cleavage of epoxides into vicinal halo alcohols and symmetrical or unsymmetrical dihalides is described using different stoichiometries of triphenylphosphine (PPh3) and N-halo succinimide (NXS) or N-halo saccharine (NXSac).
- Iranpoor, Nasser,Firouzabadi, Habib,Azadi, Roya,Ebrahimzadeh, Farzaneh
-
-
- Unexpected highly efficient ring-opening of aziridines or epoxides with iodine promoted by thiophenol
-
Ring-opening of aziridines or epoxides with iodine promoted by thiophenol afforded β-iodo amines or β-iodo alcohols in good to excellent yields under mild reaction conditions with extremely high efficiency. Georg Thieme Verlag Stuttgart.
- Wu, Jie,Sun, Xiaoyu,Sun, Wei,Ye, Shengqing
-
p. 2489 - 2491
(2008/02/11)
-
- Green protocol for the synthesis of vicinal-halohydrins from oxiranes using the [Bmim]PF6/LiX reagent system
-
Epoxides undergo rapid ring-opening with lithium halides in [bmim]PF 6 or [bmim]BF4 ionic liquids under mild and neutral conditions to afford the corresponding vic-halohydrins in high to quantitative yields. The epoxides show enhanced reactivity in ionic liquids thereby reducing reaction times and improving the yields significantly. The recovered ionic liquid can be reused in three to four subsequent runs with consistent activity.
- Yadav,Reddy,Reddy, Ch. Srinivas,Rajasekhar
-
p. 476 - 477
(2007/10/03)
-
- Selective conversion of epoxides to vic-halo alcohols and symmetrical or unsymmetrical dihalides by triphenylphosphine/2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ) in the presence of quaternary ammonium halides
-
A new method is described for the efficient and selective conversion of epoxides to vic-halo alcohols or symmetrical and unsymmetrical dihalides using PPh3/DDQ/R4NX (X = Cl, Br, I) as a mixed-reagent system.
- Iranpoor, Nasser,Firouzabadi, Habib,Aghapour, Ghasem,Nahid, Azarmidokht
-
p. 1885 - 1891
(2007/10/03)
-
- Conversion of epoxides into halohydrins with elemental halogen catalyzed by thiourea
-
A highly regioselective method for the synthesis of β-iodohydrins and β-bromohydrins by the direct ring opening of epoxides with elemental halogen in the presence of thiourea is described. This method occurs under neutral and mild conditions with high yields in various solvents even when sensitive functional groups are present.
- Sharghi, Hashem,Eskandari, Mohammad Mehdi
-
p. 8509 - 8514
(2007/10/03)
-
- High yield regioselective ring opening of epoxides using samarium chloride hexahydrate
-
Epoxides were converted to the corresponding β-azidohydrins and β-iodohydrins using SmCl3·6H2O/NaN3 in DMF and SmCl3·6H2/NaI in acetonitrile respectively. The reactions were highly regio-selective, ef
- Bhaumik, Kankan,Mali, Umesh W.,Akamanchi
-
p. 1603 - 1610
(2007/10/03)
-
- Conversion of epoxides to halohydrins with elemental halogen catalyzed by phenylhydrazine
-
The highly regioselective method for the synthesis of β-iodohydrins and β-bromohydrins by the direct ring opening of 1,2-epoxides with elemental halogen in the presence of phenylhydrazine is described. This method occurs under neutral and mild conditions with high yields in various aprotic solvents even when sensitive functional groups are present.
- Sharghi, Hashem,Eskandari, Mohammad Mehdi
-
p. 1519 - 1522
(2007/10/03)
-
- Highly regioselective ring opening of epoxides and aziridines using cerium(III) chloride
-
A wide variety of epoxides and aziridines were converted to the corresponding β-halohydrins and β-haloamines using cerium(III) chloride and the cerium(III) chloride/NaI system in acetonitrile. The reactions were highly regioselective and efficient with excellent yields under mild and neutral reaction conditions.
- Sabitha, Gowravaram,Satheesh Babu,Rajkumar,Reddy,Yadav
-
p. 3955 - 3958
(2007/10/03)
-
- Iron(III) trifluoroacetate as an efficient catalyst for solvolytic and nonsolvolytic nucleophilic ring opening of epoxides
-
Iron(III) trifluoroacetate was used as an efficient and nonhygroscopic catalyst for the alcoholysis, hydrolysis, and acetolysis of epoxides. The addition of chloride, bromide, iodide, and nitrate ions to epoxides to produce the corresponding 2-halo and 2-nitratoalkanols and also the conversion of epoxides to acetonides and thiiranes were also performed efficiently in the presence of this catalyst.
- Iranpoor, Nasser,Adibi, Hadi
-
p. 675 - 680
(2007/10/03)
-
- An easy deoxygenation of conjugated epoxides
-
An easy and high yielding transformation of epoxyketones and phenyl substituted epoxides to trans olefins in a convergent diastereoselective process is reported. The method was applied to the selective C-25 hydroxy- functionalisation of 3-keio-Δ4-cholestan-3-one, a key intermediate for the synthesis of C-25 hydroxy vitamin D3. (C) 2000 Elsevier Science Ltd.
- Righi, Giuliana,Bovicelli, Paolo,Sperandio, Anna
-
p. 1733 - 1737
(2007/10/03)
-
- Solvent-free organic reactions on silica gel supports. Facile transformation of epoxides to β-halohydrins with lithium halides
-
The reaction of epoxides with lithium halides was efficiently promoted on the surface of silica gel in the absence of any solvent to give the corresponding β-halohydrins. The reactivity of lithium halides was shown to follow the order LiI > LiBr >> LiCl, and the reactivity of LiCl was dramatically increased by adding an equivalent amount of water to this system. On the other hand a similar reaction with α,β-epoxyketones produces the α-haloenone derivatives, presumably via halohydrin intermediates. The epoxide-opening reaction of (R)-(+)-styrene oxide was also investigated to clarify the stereochemical features of this reaction.
- Kotsuki, Hiyoshizo,Shimanouchi, Tomoyasu,Ohshima, Reiji,Fujiwara, Shunsuke
-
p. 2709 - 2722
(2007/10/03)
-
- A facile conversion of epoxides to β-halohydrins with silica gel-supported lithium halides
-
A variety of epoxides are efficiently converted to the corresponding β-halohydrins with lithium halides supported on silica gel in dry media.
- Kotsuki, Hiyoshizo,Shimanouchi, Tomoyasu
-
p. 1845 - 1848
(2007/10/03)
-
- Regiocontrolled formation of iodohydrins and epoxides from Vic-diols
-
A novel method for the stereoselective preparation of iodohydrins and epoxides from stereogenic vicinal diols is described. This new high-yield methodology consists of the conversion of thionocarbonates such as 12 to the primary iodo derivative 14 with complete regiocontrol. Deprotection of ther secondary alcohol derivative in 14 gives the corresponding synthetically versatile iodohydrin 16, which is converted to epoxide 17. This methodology has been applied to complex tetraols 29 and 34. In the case of diols the transformation is conveniently carried out in high yield as a one-pot reaction.
- Adiyaman,Khanapure,Hwang,Rokach
-
p. 7367 - 7370
(2007/10/02)
-
- REACTION OF PHENYLOXIRANE WITH GRIGNARD REAGENTS IN THE PRESENCE OF TETRAISOPROPOXYTITANIUM
-
It was shown that the direction of the reaction of phenyloxirane with Grignard reagents in the presence of tetraisopropoxytitanium can be controlled, depending on the nature of the halogen and the length of the reaction.
- Sosnovskii, G. M.,Astapovich, I. V.
-
p. 1082 - 1084
(2007/10/02)
-
- Regio- and Stereoselective Synthesis of β-Halohydrins from 1,2-Epoxides with Ammonium Halides in the Presence of Metal Salts
-
A simple efficient, stereoselective, and regioselective method for the synthesis of β-chlorohydrins, β-bromohydrins, and β-iodohydrins by the direct opening of 1,2-epoxides with the corresponding ammonium halide in acetonitrile, in the presence of metal salts, is described.This new method appears to be of general use and competitive with the other methods previously reported.
- Chini, Marco,Crotti, Paolo,Gardelli, Cristina,Macchia, Franco
-
p. 3805 - 3812
(2007/10/02)
-
- An easy procedure for the highly regioselective conversion of epoxides to halohydrins
-
Several epoxides and epoxy alcohols have been opened to the corresponding halohydrins by lithium halides with Amberlyst in CH3CN at room temperature: the reaction proceeds in quantitative yields with high degree of regioselectivity.
- Bonini,Giuliano,Righi,Rossi
-
p. 1863 - 1870
(2007/10/02)
-
- A Highly Regioselective Conversion of Epoxides to Halohydrins by Lithium Halides
-
Lithium halides in the presence of an acid (pKa 13) react with epoxides regioselectively to give vicinal halohydrins in high yields.The simplicity and convenience of this procedure makes it attractive for large scale synthesis.
- Bajwa, Joginder S.,Anderson, Robert C.
-
p. 3021 - 3024
(2007/10/02)
-
- THE DIRECT CONVERSION OF EPOXIDES INTO ALKENES via IODOHYDRINS BY in situ GENERATED HI
-
Epoxides are easily converted into iodohydrins and alkenes are obtained from either epoxides or iodohydrins by treatment with HI, generated in situ from Ph3P*I2 in moist CH3CN.
- Garlaschelli, Luigi,Vidari, Giovanni
-
p. 251 - 254
(2007/10/02)
-
- An Easy and Efficient Epoxide Opening to give Halohydrins using Tin(II) Halides
-
Epoxides are readily converted into halohydrins by tin(II) halides in a variety of solvents.
- Einhorn, Cathy,Luche, Jean-Louis
-
p. 1368 - 1369
(2007/10/02)
-