- 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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- Synthesis of 2-Arylpiperidines via pd-catalyzed arylation of aza-Achmatowicz rearrangement products with arylboronic acids
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The first Pd-catalyzed arylation of aza-Achmatowicz rearrangement products with arylboronic acids is achieved, providing versatile 2-Aryldihydropyridinones for facile synthesis of highly functionalized 2-Arylpiperidines. Key to this arylation is the use of non-phosphine-ligand palladium precatalyst. The substrate scope is demonstrated with >26 examples, and the utility of 2-Aryldihydropyridinones is illustrated by the synthesis of a small collection of 2-Arylpiperidines with substituents or functional groups at any carbon (C2-C6) as well as two NK1 receptor antagonists (+)-CP-999,94 and (+)-L-733,060.
- Zhao, Guodong,Canterbury, Daniel P.,Taylor, Alexandria P.,Cheng, Xiayun,Mikochik, Peter,Bagley, Scott W.,Tong, Rongbiao
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p. 458 - 463
(2020/01/21)
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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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- 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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supporting information
p. 98 - 101
(2019/12/25)
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- Two Distinct Ag(I)- And Au(I)-Catalyzed Olefinations between α-Diazo Esters and N-Boc-Derived Imines
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Metal-catalyzed reactions between α-diazo esters and imines were well-known to yield aziridine derivatives exclusively. This work reports two new olefination reactions between N-Boc-derived (Boc = tert-Butyloxycarbonyl) imines and α-diazo esters with Ag(I) and Au(I) catalysts, respectively. Our mechanistic studies reveal that these new olefinations involve an initial attack of diazo esters on metal/imine complexes to form Mannich-addition intermediates, which subsequently afford α-aryl-β-aminoacrylates via a Roskamp reaction, or to form β-aryl-β-aminoacrylates via the formation of silver carbenes.
- Kardile, Rahul Dadabhau,Liu, Rai-Shung
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p. 6452 - 6456
(2019/09/06)
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- Development of a cyclosporin A derivative with excellent anti-hepatitis C virus potency
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Synthetic modification of cyclosporin A at P3-P4 positions led to the discovery of NIM258, a next generation cyclophilin inhibitor with excellent anti-hepatitis C virus potency, with decreased transporter inhibition, and pharmacokinetics suitable for coad
- Fu, Jiping,Becker, Christopher,Cao, Li,Capparelli, Michael,Denay, Regis,Fujimoto, Roger,Gai, Yu,Gao, Zhaobo,Guenat, Christian,Karur, Subramanian,Kim, Hongyong,Li, Weikuan,Li, Xiaolin,Li, Wei,Lochmann, Thomas,Lu, Amy,Lu, Peichao,Luneau, Alexandre,Meier, Nicole,Mergo, Wosenu,Ng, Simon,Parker, David,Peng, Yunshan,Riss, Bernard,Rivkin, Alexey,Roggo, Silvio,Schroeder, Harald,Schuerch, Friedrich,Simmons, Robert L.,Sun, Feng,Sweeney, Zachary K.,Tjandra, Meiliana,Wang, Michael,Wang, Ruidong,Weiss, Andrew H.,Wenger, Nicolas,Wu, Quanbing,Xiong, Xin,Xu, Su,Xu, Wenjian,Yifru, Aregahegn,Zhao, Jibin,Zhou, Jianguang,Zürcher, Christian,Gallou, Fabrice
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p. 957 - 969
(2018/02/20)
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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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- 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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- 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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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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- 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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- 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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- 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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