- Solid-phase synthesis of 4-methylene pyrrolidines and allylic amines using palladium-activated allylic linkers
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The solid-phase synthesis of 4-methylene pyrrolidines and allylic amines has been achieved using palladium-catalysed nucleophilic cleavage of allylic linkages. Six pyrrolidines were synthesised in five steps from a carboxyethyl resin 20, where the key transformations included a Lewis-acid promoted imino-Sakurai type reaction and reductive alkylation prior to the final palladium-catalysed cyclisation cleavage of the allylic carboxylate linkage. Allylic carboxylate resin 22 was also shown to undergo "traceless" cleavage using various hydride sources in the presence of catalytic palladium. A more robust allylic ether linkage was also investigated. Starting from a phenol resin 36, a number of 3-aryl-allylaniines were prepared using a palladium-catalysed nucleophilic cleavage reaction.
- Brown, Richard C.D.,Fisher, Martyn L.,Brown, Lynda J.
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- Direct enantioselective Mannich reactions of α-azido cyclic ketones: Asymmetric construction of chiral azides possessing an α-quaternary stereocenter
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Direct enantioselective Mannich reactions of α-azido cyclic ketones with aldimines are realized through chiral phosphoric acid catalysis, which generate chiral azides possessing an α-quanternary stereocenter with complete regioselectivities and high diast
- Ye, Xueqian,Pan, Yongkai,Yang, Xiaoyu
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- Diastereoselective Ugi reaction of chiral 1, 3-aminoalcohols derived from an organocatalytic Mannich reaction
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Enantiomerically pure β-aminoalcohols, produced through an organocatalytic Mannich reaction, were subjected to an Ugi multi-component reaction under classical or Lewis acid-promoted conditions with diastereoselectivities ranging from moderate to good. Thi
- Caputo, Samantha,Basso, Andrea,Moni, Lisa,Riva, Renata,Rocca, Valeria,Banfi, Luca
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- Enantioselective, Catalytic Multicomponent Synthesis of Homoallylic Amines Enabled by Hydrogen-Bonding and Dispersive Interactions
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We report a one-step catalytic, enantioselective method for the preparation of homoallylic N-Boc amines directly from acetals. Reactive iminium ion intermediates are generated in situ through the combination of an acetal, a chiral thiourea catalyst, trialkylsilyl triflate, and N-Boc carbamate and are subsequently trapped by a variety of allylsilane nucleophiles. No homoallylic ether byproducts are detected, consistent with allylation of the iminium intermediate being highly favored over allylation of the intermediate oxocarbenium ion. Acetals derived from aromatic aldehydes possessing a variety of functional groups and substitution patterns yield homoallylic amines with excellent levels of enantiomeric enrichment. Experimental and computational data are consistent with an anchoring hydrogen-bond interaction between the protioiminium ion and the amide of the catalyst in the enantiodetermining transition state, and with stereodifferentiation achieved through specific noncovalent interactions (NCIs) with the catalyst pyrenyl moiety. Evidence is provided that the key NCI in the major pathway is a π-stacking interaction, contrasting with the cation-πinteractions invoked in previously studied reactions promoted by the same family of aryl-pyrrolidino-H-bond-donor catalysts.
- Ronchi, Elisabetta,Paradine, Shauna M.,Jacobsen, Eric N.
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supporting information
p. 7272 - 7278
(2021/05/26)
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- Visible-Light-Induced Cycloaddition of α-Ketoacylsilanes with Imines: Facile Access to β-Lactams
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We report the synthesis of β-lactams from α-ketoacylsilanes and imines, which proceeds via a formal [2+2] photochemical cycloaddition with in situ generation of siloxyketene. This mild and operationally simple reaction proceeds in an atom-economic fashion with broad substrate scope, including aldimines, ketimines, hydrazones, and fused nitrogen heterocycles, affording a variety of important β-lactams with satisfactory diastereoselectivities in most cases. This reaction also features good functional-group tolerance, facile scalability and product diversification. Experimental and computational studies suggest that α-ketoacylsilanes can serve as photochemical precursors by engaging in a 1,3 silicon shift to the distal carbonyl group.
- Ye, Jian-Heng,Bellotti, Peter,Paulisch, Tiffany O.,Daniliuc, Constantin G.,Glorius, Frank
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supporting information
p. 13671 - 13676
(2021/05/11)
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- Synthetic method of dapoxetine and intermediate thereof
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The invention discloses a synthetic method of dapoxetine and its intermediate, i.e., (S)-3-(tert-butyloxycarbonyl)amino-3-phenylpropanol as shown in a formula 5 which is described in the specification. The synthetic method of (S)-3-(tert-butyloxycarbonyl)amino-3-phenylpropanol is as shown in a synthesis route which is described in the specification, wherein a compound 3 and acetaldehyde are subjected to a Mannich reaction in an organic solvent under the action of a supramolecular catalyst constructed by a chiral catalyst and a polymer so as to obtain a compound 4, and the polymer is at least one selected from of the group consisting of PEG 200, PEG 400, PEG 600, MeOPEG 750, PEG 800, PEG 1000, PPG 800 and PPG 1000. The dapoxetine is synthesized from the (S)-3-(tert-butyloxycarbonyl)amino-3-phenylpropanol prepared by using the above method according to steps as shown in the synthesis route. The synthetic method of dapoxetine and the intermediate thereof has the characteristics of usage of cheap and easily available raw materials, high yield and low cost, and is more beneficial to industrial production.
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- Enantioselective Construction of Sulfur-Containing Tetrasubstituted Stereocenters via Asymmetric Functionalizations of α-Sulfanyl Cyclic Ketones
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Asymmetric functionalizations of α-sulfanyl cyclic ketones were realized via chiral phosphoric acid catalyzed enantioselective addition reactions with aldimines, azodicarboxylates and allenamides. A series of chiral organosulfur compounds possessing sulfur-containing tetrasubstituted stereocenters were accessed via these methods, with excellent regioselectivities and high stereoselectivities. (Figure presented.).
- Ye, Xueqian,Pan, Yongkai,Chen, Yunrong,Yang, Xiaoyu
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p. 3374 - 3379
(2020/07/16)
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- γ-Selective Vinylogous Aza-Morita-Baylis-Hillman Reaction with N -Carbamoylimines
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Vinylogous aza-Morita-Baylis-Hillman (aza-MBH) reactions of a vinylcyclopentenone with N -Boc imines provide the corresponding γ-adducts in high regioselectivity (10 examples). While the corresponding reactions with N -Ts imines give the α-adducts and γ-a
- Gondo, Naruhiro,Tanigaki, Yusuke,Ueda, Yoshihiro,Kawabata, Takeo
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p. 398 - 402
(2020/02/27)
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- Silver-Catalyzed Enantioselective Mannich Reaction of Diazoacetate Esters with N-Boc Aldimines
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The highly enantioselective Mannich reaction of diazoacetate esters with N-Boc aldimines catalyzed by silver(I) triflate in the presence of (R)-DM-SEGPHOS is reported. The reaction is broad in scope with respect to the (hetero)aromatic aldehyde-derived al
- Robertson, Gerard P.,Farley, Alistair J. M.,Dixon, Darren J.
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p. 2785 - 2792
(2020/02/04)
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- Direct Catalytic Asymmetric Mannich-Type Reaction en Route to α-Hydroxy-β-amino Acid Derivatives
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A direct catalytic Mannich-type reaction of α-oxygen-functionalized amides was achieved. The use of 7-azaindoline amide was crucial to facilitate direct enolization and subsequent stereoselective addition to imines in a cooperative catalytic system comprising a soft Lewis acid and Br?nsted base. The operationally simple room-temperature protocol furnished a syn-Mannich adduct with high stereoselectivity. Divergent functional group transformation of the amide moiety of the product allowed for expeditious access to enantioenriched syn-configured α-hydroxy-β-amino carboxylic acid derivatives, highlighting the synthetic utility of the present catalysis.
- Sun, Bo,Pluta, Roman,Kumagai, Naoya,Shibasaki, Masakatsu
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p. 526 - 529
(2018/02/10)
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- Synthesis of highly substituted 2-spiropiperidines
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2-Spiropiperidines are a highly desirable, yet under represented structure in drug discovery. 2-Spiropiperidines were synthesised in either a two-pot or one-pot reaction. In the two-pot reaction, the addition of a Weiler dianion to N-Boc imines, followed by deprotection and in situ condensation with a cyclic ketone generated functionalised 2-spiropiperidines in good to excellent yields. In the one-pot reaction, the addition of Chan's diene to N-Boc imines under Maitland-Japp conditions, followed by the addition of sodium bicarbonate and a cyclic ketone formed functionalised 2-spiropiperidines in moderate to good yields.
- Griggs, Samuel D.,Thompson, Nathan,Tape, Daniel T.,Fabre, Marie,Clarke, Paul A.
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p. 6663 - 6674
(2018/09/29)
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- Copper-catalyzed borylative coupling of vinylazaarenes and N-Boc imines
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Cu-catalyzed three-component couplings of vinylazaarenes, B2(pin)2, and N-Boc imines are described. Oxidation of the initially formed boronate gives azaarene-containing, Boc-protected amino alcohols with reasonable to good diastereoselectivities.
- Smith, Joshua J.,Best, Daniel,Lam, Hon Wai
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p. 3770 - 3772
(2016/03/22)
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- Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions
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The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.
- Novacek, Johanna,Roiser, Lukas,Zielke, Katharina,Robiette, Rapha?l,Waser, Mario
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p. 11422 - 11428
(2016/08/03)
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- Efficient synthesis of α-(N-Boc)aminoamides by addition of a carbamoylsilane to N-Boc-imines
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N,N-Dimethylcarbamoyl(trimethyl)silane reacted with N-Boc-imines in anhydrous benzene under catalysts-free conditions to afford N-Boc-protected α-amino amides in good yields (72-89%). The electronic property and the steric hindrance of substituent on the N-Boc-imines affected the reaction.
- Guo, Qilin,Wen, Xueping,Chen, Jianxin
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p. 8117 - 8122
(2016/11/19)
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- Enantioselective copper-catalyzed reductive coupling of vinylazaarenes with n -boc aldimines
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The diastereo- and enantioselective reductive coupling of vinylazaarenes with N-Boc aldimines is described. The reactions proceed using chiral copper-bisphosphine complexes in the presence of TMDS as a hydride source to give reductive coupling products in moderate to high enantioselectivities.
- Choi, Bonnie,Saxena, Aakarsh,Smith, Joshua J.,Churchill, Gwydion H.,Lam, Hon Wai
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p. 350 - 354
(2015/02/19)
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- Disulfonimide-Catalyzed Asymmetric Synthesis of δ-Amino-β-Keto Esters
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A chiral disulfonimide-catalyzed asymmetric synthesis of δ-amino-β-keto esters via a vinylogous Mukaiyama-Mannich reaction of the Chan diene with N-Boc imines has been developed. The desired products were obtained in good to excellent yields and enantioselectivities.
- Wang, Qinggang,List, Benjamin
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p. 807 - 809
(2015/03/30)
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- Chiral ureas and thioureas supported on polystyrene for enantioselective aza-Henry reactions under solvent-free conditions
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Novel bifunctional ureas and thioureas immobilized on sulfonylpolystyrene have been prepared as recoverable and reusable organocatalysts and have been used in the stereoselective aza-Henry reaction under solvent-free conditions. The activity and stereoselection of the catalysts are dependent on the length of the tether bridging the active site and the polymer, the catalyst derived from 1,6-hexane diamine being the best one. It has also been demonstrated that the supported catalysts are more effective than the homologous soluble catalysts.
- Pedrosa, Rafael,Andrés, José M.,ávila, Deisy P.,Ceballos, Miriam,Pindado, Rodrigo
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p. 2217 - 2225
(2015/04/22)
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- Copper(I)-Catalyzed Asymmetric Pinacolboryl Addition of N-Boc-imines Using a Chiral Sulfoxide - Phosphine Ligand
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Highly efficient and enantioselective copper(I)-catalyzed pinacolboryl addition of N-Boc-imines is reported. By using a single chiral sulfoxide-(dialkyl)phosphine (SOP) ligand, both enantiomeric isomers of α-amino boronic esters were obtained through an achiral counteranion switch.
- Wang, Ding,Cao, Peng,Wang, Bing,Jia, Tao,Lou, Yazhou,Wang, Min,Liao, Jian
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p. 2420 - 2423
(2015/05/27)
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- Development of Non-C2-symmetric ProPhenol Ligands. the Asymmetric Vinylation of N-Boc Imines
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The development and application of a new generation of non-C2-symmetric ProPhenol ligands is reported herein. Rational design of the ProPhenol ligand paved the way to the first catalytic and asymmetric vinylation of N-Boc imines via hydrozirconation giving rise to valuable allylic amines in excellent yields and enantioselectivities. The utility of this method was demonstrated by developing the shortest reported asymmetric synthesis of the selective serotonine reuptake inhibitor (SSRI) (-)-dapoxetine.
- Trost, Barry M.,Hung, Chao-I,Koester, Dennis C.,Miller, Yan
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p. 3778 - 3781
(2015/08/18)
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- Lanthanide coordination polymer constructed from 2,2′-bipyridyl-4,4′-dicarboxylic acid: Structure, catalysis and fluorescence
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Two new isostructural lanthanide coordination polymers (Ln-CPs) [Ln2(bpdc)3(DMF)2] (Ln = Tb for 1, Eu for 2) with two kinds of one-dimensional channels along the a axis, were synthesized by 2,2′-bipyridyl-4,4′-dicarboxylic acid (H2bpdc) under solvothermal conditions. With exposed Lewis acid Ln3+ centers, 1 as a heterogeneous catalyst shows good catalytic reactivity and selectivity for the Strecker reaction affording medium to excellent conversion yields. Luminescent studies illustrate that 1 and 2 show intensive green and red luminescence triggered by efficient antenna effect of ligands under UV light, respectively. Moreover, 1 exhibits sensitive fluorescent response to Cu2+ in DMF solution.
- Wang, Shengyan,Xu, Jianing,Zheng, Jifu,Chen, Xiaodong,Shan, Liang,Gao, Lijuan,Wang, Li,Yu, Miao,Fan, Yong
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supporting information
p. 81 - 86
(2015/09/15)
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- Diastereo- and enantioselective addition of anilide-functionalized allenoates to N-acylimines catalyzed by a pyridylalanine-based peptide
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A selective peptide-catalyzed addition of allenic esters to N-acylimines is reported. Tetrasubstituted allenes were achieved with up to 42:1 diastereomeric ratio and 94:6 enantiomeric ratio (up to 99:1 er after recrystallization of the major diastereomer). An exploration of the role of individual amino acids within the peptide was undertaken. The scope of the reaction was explored and revealed heightened reactivity with thioester-containing allenes. A mechanistic framework that may account for the observed reactivity is also described.
- Mbofana, Curren T.,Miller, Scott J.
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p. 3285 - 3292
(2014/03/21)
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- Construction of chiral quaternary carbon center via catalytic asymmetric aza-Henry reaction with α-substituted nitroacetates
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The catalytic enantioselective aza-Henry reaction of N-Boc aldimines 2 and 2-nitropropionic acid ethyl ester 3 in the mixed solvents of toluene-saturated brine (10:1) was catalyzed by cinchona quaternary ammonium salts to form a new quaternary carbon center. High yields (up to 90%), and excellent enantioselectivities (up to 99% ee) and diastereoselectivity ratio (up to 22:1) were successfully obtained with mild conditions. This journal is the Partner Organisations 2014.
- Li, Minghua,Ji, Nan,Lan, Ting,He, Wei,Liu, Rui
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p. 20346 - 20350
(2014/06/09)
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- Asymmetric disulfonimide-catalyzed synthesis of δ-amino-β-ketoester derivatives by vinylogous Mukaiyama-Mannich reactions
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An organocatalytic asymmetric synthesis of δ-amino-β-ketoester derivatives has been developed. A chiral disulfonimide (DSI) serves as a highly efficient precatalyst for a vinylogous Mukaiyama-Mannich reaction of readily available dioxinone-derived silylox
- Wang, Qinggang,Van Gemmeren, Manuel,List, Benjamin
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p. 13592 - 13595
(2015/01/09)
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- Enantioselective Mannich reaction of β-keto esters with aromatic and aliphatic imines using a cooperatively assisted bifunctional catalyst
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An efficient urea-enhanced thiourea catalyst enables the enantioselective Mannich reaction between β-keto esters and N-Boc-protected imines under mild conditions and minimal catalyst loading (1-3 mol %). Aliphatic and aromatic substituents are tolerated on both reaction partners, affording the products in good enantiomeric purity. The corresponding β-amino ketones can readily be accessed via decarboxylation without loss of enantiomeric purity.
- Neuvonen, Antti J.,Pihko, Petri M.
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supporting information
p. 5152 - 5155
(2015/01/08)
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- Asymmetric mannich reaction of malonates with aldimines using YbIII-pybox complexes supported on self-assembled organic-inorganic hybrid silica with an imidazolium framework
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Yb(OTf)3/iPr-pybox (3b) immobilized on a self-assembled organic-inorganic hybrid silica with ionic liquid phase (SAILP) (Catalyst A) behaves as an efficient and recyclable catalyst in the enantioselective Mannich reaction of malonate esters wit
- Karimi, Babak,Jafari, Ehsan,Enders, Dieter
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supporting information
p. 7253 - 7258
(2015/02/02)
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- Asymmetric synthesis of anti -β-amino-α-hydroxy esters via dynamic kinetic resolution of β-amino-α-keto esters
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A method for the asymmetric synthesis of enantioenriched anti-α-hydroxy-β-amino acid derivatives by enantioconvergent reduction of the corresponding racemic α-keto esters is presented. The requisite α-keto esters are prepared via Mannich addition of ethyl
- Goodman, C. Guy,Do, Dung T.,Johnson, Jeffrey S.
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supporting information
p. 2446 - 2449
(2013/06/27)
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- Highly efficient catalytic enantioselective mannich reaction of malonates with N-tert-butoxycarbonyl imines by using Yb(OTf)3/pybox catalysts at room temperature
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Go Mannich! A highly efficient and enantioselective method for the direct asymmetric reaction of dibenzyl malonate with N-tert-butoxycarbonyl aldimines in the presence of Yb(OTf)3 and iPr-pybox complexes is described (see scheme; pybox=pyridine
- Karimi, Babak,Jafari, Ehsan,Enders, Dieter
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supporting information
p. 10142 - 10145
(2013/09/02)
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- The homo-PADAM protocol: Stereoselective and operationally simple synthesis of α-oxo- or α-hydroxy-γ-acylaminoamides and chromanes
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A straightforward and fully stereoselective synthesis of a new class of peptidomimetics, that is α-oxo-γ-acylaminoamides, was achieved starting from various benzaldehydes by a sequence of 1) an asymmetric organocatalytic Mannich reaction, 2) a Passerini multicomponent reaction, 3) an amine deprotection-acyl migration protocol, and 4) a final oxidation. The whole sequence can be performed without purification of the intermediates and represents the first example of a homo-Passerini-amine deprotection-acyl migration (PADAM) strategy. Highly stereoselective reduction of the α-oxo-γ-acylaminoamides afforded α-hydroxy-γ- acylaminoamides as well. In some cases both diastereomers were obtained by simply changing the reducing agent. Finally, starting from protected salicylaldehyde, the same sequence, followed by a Mitsunobu cyclization, afforded highly substituted chromanes. Copyright
- Morana, Fabio,Basso, Andrea,Riva, Renata,Rocca, Valeria,Banfi, Luca
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p. 4563 - 4569
(2013/04/24)
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- Diastereo- and enantioselective Pd(II)-catalyzed additions of 2-alkylazaarenes to N -boc imines and nitroalkenes
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A chiral Pd(II)-bis(oxazoline) complex was found to be highly effective in promoting the first direct diastereo- and enantioselective addition of alkylazaarenes to N-Boc aldimines and nitroalkenes under mild conditions. Deprotection of Boc-protected products proceeded readily to provide amines in high yields.
- Best, Daniel,Kujawa, Szymon,Lam, Hon Wai
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p. 18193 - 18196
(2013/01/15)
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- One-pot catalytic enantioselective synthesis of tetrahydropyridines via a nitro-mannich/hydroamination cascade
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The highly enantioselective preparation of synthetically useful tetrahydropyridine derivatives employing a one-pot nitro-Mannich/hydroamination cascade is reported. This approach utilizes an asymmetric organocatalytic nitro-Mannich reaction followed by a gold-catalyzed alkyne hydroamination/ isomerization sequence that yields the desired tetrahydropyridines in good yields and high diastereo- and enantioselectivities.
- Barber, David M.,Sanganee, Hitesh J.,Dixon, Darren J.
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p. 5290 - 5293
(2013/01/15)
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- One-pot synthesis of α-amino acids from CO2 using a bismetal reagent with Si-B bond
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In the presence of 1.1 equiv of PhMe2Si-Bpin, 5 equiv of CsF, and 20 mol % of TsOH·H2O, precursors of N-Boc-imines can be converted into the corresponding α-aryl or α-alkenyl glycine derivatives under gaseous CO2 in moderate-to-high yields with a single operation. α-Isobutenyl glycine thus obtained can be further derivatized into various types of α-amino acids including N-Boc-leucine, serine, and glycine derivatives in short steps.
- Mita, Tsuyoshi,Chen, Jianyang,Sugawara, Masumi,Sato, Yoshihiro
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p. 6202 - 6205
(2013/02/23)
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- One-pot synthesis of α-amino acids from imines through CO2 incorporation: An alternative method for strecker synthesis
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Itas a gas: A novel one-pot process for the synthesis of α-amino acids from imine equivalents using CO2 gas as a carbon source has been developed. This reaction was made possible by the reagent combination of TMSSnBu3 and CsF (see scheme). Three successive reactions (imine formation, stannylation, and carboxylation) proceeded in the same flask under these conditions to give products in up to 79 % yield. Boc=tert-butoxycarbonyl, TMS=trimethylsilyl.
- Mita, Tsuyoshi,Chen, Jianyang,Sugawara, Masumi,Sato, Yoshihiro
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p. 1393 - 1396
(2011/04/22)
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- Catalytic asymmetric synthesis of trisubstituted aziridines
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A method is described which provides for the direct asymmetric catalytic synthesis of trisubstituted aziridines from imines and diazo compounds. While unactivated imines were not reactive to α-diazo carbonyl compounds in which the diazo carbon was disubstituted, N-Boc imines react with both α-diazo esters and α-diazo-N-acyloxazolidinones to give trisubstituted aziridines with excellent diastereo- and enantioselectivities.
- Huang, Li,Wulff, William D.
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p. 8892 - 8895
(2011/08/04)
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- A practical, one-pot multicomponent synthesis of α-amidosulfides and their application as latent N-acylimines in the Friedel-Crafts reaction
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A novel one-pot, three-component synthesis of N-acyl or N-carbamoyl-α-amidosulfides 4 is described. The three-component reaction of aldehydes 1, primary carbamates (or amides) 2 and phenylsulfinic acid (6a) afforded α-amidosulfones 7, which after addition
- George, Nicolas,Bekkaye, Mathieu,Masson, Geraldine,Zhu, Jieping
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p. 3695 - 3699
(2011/09/16)
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- Practical synthesis of N -Boc- and N -Cbz-α-amido stannanes from α-amido sulfones using TMSSnBu3 and CsF
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Chemical equations presented. In the presence of TMSSnBu3 and CsF, stannylation of N-Boc- and N-Cbz-α-amido sulfones proceeded very well to afford the corresponding α-amido stannanes in moderate-to-high yields. This reaction tolerated α-aryl-,
- Mita, Tsuyoshi,Higuchi, Yuki,Sato, Yoshihiro
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scheme or table
p. 2354 - 2357
(2011/06/24)
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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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- Quantification of the electrophilic reactivities of aldehydes, imines, and enones
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The rates of the epoxidation reactions of aldehydes, of the aziridination reactions of aldimines, and of the cyclopropanation reactions of α,β-unsaturated ketones with aryl-stabilized dimethylsulfonium ylides have been determined photometrically in dimethyl sulfoxide (DMSO). All of these sulfur ylide-mediated cyclization reactions as well as the addition reactions of stabilized carbanions to N-tosyl-activated aldimines have been shown to follow a second-order rate law, where the rate constants reflect the (initial) CC bond formation between nucleophile and electrophile. The derived second-order rate constants (log k2) have been combined with the known nucleophilicity parameters (N, sN) of the aryl-stabilized sulfur ylides 4a,b and of the acceptor-substituted carbanions 4c-h to calculate the electrophilicity parameters E of aromatic and aliphatic aldehydes (1a-i), N-acceptor-substituted aromatic aldimines (2a-e), and α,β-unsaturated ketones (3a-f) according to the linear free-energy relationship log k 2 = sN(N + E) as defined in J. Am. Chem. Soc.2001, 123, 9500-9512. The data reported in this work provide the first quantitative comparison of the electrophilic reactivities of aldehydes, imines, and simple Michael acceptors in DMSO with carbocations and cationic metal-π complexes within our comprehensive electrophilicity scale.
- Appel, Roland,Mayr, Herbert
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body text
p. 8240 - 8251
(2011/07/29)
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- Highly enantioselective titanium-catalyzed cyanation of imines at room temperature
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(Figure presented) A highly active and enantioselective titanium-catalyzed cyanatlon of imines at room temperature Is described. The catalyst used Is a partially hydrolyzed titanium alkoxide (PHTA) precatalyst together with a readily available N-salicyl-β-aminoalcohol ligand. Up to 98% ee was obtained with quantitative yields In 15 min of reaction time using 5 mol % of the catalyst. Various N-protecting groups such as benzyl, benzhydryl, Boc, and PMP are tolerated.
- Seayad, Abdul Majeed,Ramalingam, Balamurugan,Yoshinaga, Kazuhiko,Nagata, Takushi,Chai, Christina L. L.
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supporting information; experimental part
p. 264 - 267
(2010/03/24)
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- Highly efficient and diastereoselective synthesis of 1,3-oxazolidines featuring a palladium-catalyzed cyclization reaction of 2-butene-1,4-diol derivatives and imines
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A palladium-catalyzed protocol for effective synthesis of 1,3-oxazolidines has been reported. This method is featured by the high diastereoselectivity (dr up to >98/2) and using the readily available 2-butene-1,4-diol derivatives and imines as substrates.
- Chen, Dongxu,Chen, Xiaoyi,Du, Taiping,Kong, Lichun,Zhen, Renwei,Zhen, Shaocheng,Wen, Yihang,Zhu, Gangguo
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supporting information; experimental part
p. 5131 - 5133
(2010/11/18)
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- Heterobimetallic transition metal/rare earth metal bifunctional catalysis: A Cu/Sm/schiff base complex for Syn -selective catalytic asymmetric nitro-mannich reaction
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The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)2/Sm(O-iPr)3/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)3, we reoptimized the catalyst preparation method, and a catalyst derived from Sm 5O(O-iPr)13 showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)3. The optimal system with Sm5O(O-iPr)13 was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm5O(O-iPr)13.
- Handa, Shinya,Gnanadesikan, Vijay,Matsunaga, Shigeki,Shibasaki, Masakatsu
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supporting information; experimental part
p. 4925 - 4934
(2010/06/18)
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- A novel bis-thiourea organocatalyst for the asymmetric aza-Henry reaction
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A novel bis-thiourea/2,2′-diaminobinaphthalene (BINAM)-based catalyst for the asymmetric aza-Henry reaction has been developed. This catalyst promotes the reaction of N-Boc imines with nitroalkanes to afford β-nitroamines with good yields and high enantioselectivities. This catalyst has the advantage that it can be prepared in a single step from commercially available materials. A model is proposed for the catalyst action where both components of the reaction are activated simultaneously by hydrogen bonding. Regardless of the mechanism, the success of the present catalyst demonstrates the potential of bis-thioureas as an interesting class of relatively unexplored catalysts.
- Rampalakos, Constantinos,Wulff, William D.
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supporting information; experimental part
p. 1785 - 1790
(2009/08/07)
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- N-carbamate protected α-amidoalkyl-p-tolylsulfones: Convenient substrates in the aza-Morita-Baylis-Hillman reaction
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(Chemical Equation Presented) An efficient and practical one-pot approach to aza-Morita-Baylis-Hillman adducts has been developed. The reaction occurs between N-Boc or N-Cbz imines, generated in situ from stable and easy to handle N-Boc or N-Cbz protected
- Gajda, Anna,Gajda, Tadeusz
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experimental part
p. 8643 - 8646
(2009/04/11)
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- Enantioselective aza-Henry reactions assisted by ZnII and N-methylephedrine
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(Chemical Equation Presented) Hooray aza-Henry! A combination of zinc triflate, an amine base, and (-)-N-methylephedrine (NME), which can be easily recovered and reused, leads to high enantioselectivities in the aza-Henry reaction of N-Boc-protected aldimines and nitromethane (see scheme; Boc = tert-butyloxycarbonyl).
- Palomo, Claudio,Oiarbide, Mikel,Halder, Rajkumar,Laso, Antonio,Lopez, Rosa
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p. 117 - 120
(2007/10/03)
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- Asymmetric mannich reactions with α-silylated trimethylsilyl enol ethers and N-alkoxycarbonyl imines
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The Mannich reaction of enantiomerically pure α-dimethylthexylsilylated trimethylsilyl enol ether (Z,S)-2 with titanium complexes of N-alkoxycarbonyl imines afforded α′-silylated αβ-disubstituted β-amino ketones (S,R,S)-4a-e in good to excellent yields (70-92percent) and diastereomeric excesses (de ≥ 96percent). Removal of the directing silyl group gave N-protected and anti-configured β-amino ketones (R,S)-5a-e in excellent yields (90-95percent) and stereoselectivities (de, ee ≥ 96percent- > 98percent).
- Enders, Dieter,Oberbo?rsch, Stefan
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p. 471 - 473
(2007/10/03)
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- N-alkyloxycarbonyl-3-aryloxaziridines: Their preparation, structure, and utilization as electrophilic amination reagents
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This paper reports the synthesis of a series of N-protected oxaziridines (N-Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N-alkoxycarbonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N-protected fragment to primary and secondary amines to give protected hydrazines in fair to excelent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N-protected α-hydrazino acids. Enolates are C-aminated to give N-protected α-amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.
- Vidal, Joelle,Damestoy, Stephanie,Guy, Laure,Hannachi, Jean-Christophe,Aubry, Andre,Collet, Andre
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p. 1691 - 1709
(2007/10/03)
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- Highly stereocontrolled and efficient preparation of the protected, esterification-ready docetaxel (Taxotere) side chain
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A high-yield synthesis of the p-methoxybenzylidene-protected docetaxel (Taxotere) side chain, a useful derivative for efficient, epimerization-free esterification of the 7,10-bis[(trichloroethoxy)carbonyl] derivative of 10-desacetylbaccatin III for the preparation of docetaxel, has been effected; the C-4 and C-5 stereocenters of the 1,3-oxazolidine are generated with complete (≥99%) stereocontrol whereas that at C-2 is produced with 96% selectivity.
- Kanazawa,Denis,Greene
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p. 1238 - 1240
(2007/10/02)
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- Electrophilic Amination: Preparation and Use of N-Boc-3-(4-cyanophenyl)oxaziridine, a New Reagent That Transfers a N-Boc Group to N- and C-Nucleophiles
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We describe the preparation of the title compound 2b via aza-Wittig reaction of N-Boc-triphenyliminophosphorane (6) with 4-cyanobenzaldehyde followed by Oxone oxidation of the resulting imine 5b.Oxaziridine 2b is a stable, crystalline solid, which transfers under mild conditions its N-Boc fragment to primary and secondary amines (to give Nβ-Boc-hydrazines) and enolates (to give N-Boc-amino drivatives).
- Vidal, Joelle,Guy, Laure,Sterin, Sebastien,Collet, Andre
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p. 4791 - 4793
(2007/10/02)
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