- Electrochemical Umpolung C-H Functionalization of Oxindoles
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Herein, we present a general electrochemical method to access unsymmetrical 3,3-disubstituted oxindoles by direct C-H functionalization where the oxindole fragment behaves as an electrophile. This Umpolung approach does not rely on stoichiometric oxidants and proceeds under mild, environmentally benign conditions. Importantly, it enables the functionalization of these scaffolds through C-O, and by extension to C-C or even C-N bond formation.
- Pastor, Miryam,Vayer, Marie,Weinstabl, Harald,Maulide, Nuno
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supporting information
p. 606 - 612
(2022/01/12)
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- Enantioselective vinylogous aldol reaction of acylphosphonates with 3-alkylidene oxindoles
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A simple strategy for yielding chiral tertiary α-hydroxy phosphonates that integrates two highly biologically relevant scaffolds namely 3-alkylidene-2-oxindoles and phosphonates has been described. The hydrogen bonding ability of the bifunctional thiourea catalyst allows simultaneous dual activation of a vinylogous oxindole nucleophile and an acylphosphonate electrophile, affording hydroxyphosphonato-3-alkylidene-2-oxindoles as aldol adducts in high yields (up to 92%) with excellent stereocontrol (up to 99% ee).
- Jaiswal, Manish K.,Singh, Sanjay,Singh, Ravi P.
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supporting information
p. 7861 - 7866
(2021/09/28)
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- Harnessing Applied Potential: Selective β-Hydrocarboxylation of Substituted Olefins
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The construction of carboxylic acid compounds in a selective fashion from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, β-addition to styrenes is underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of alkenes that overcomes the limitations of current transition metal and photochemical approaches. The reported method allows unprecedented direct access to carboxylic acids derived from β,β-trisubstituted alkenes, in a highly regioselective manner.
- Alkayal, Anas,Buckley, Benjamin R.,Malkov, Andrei V.,Montanaro, Stephanie,Tabas, Volodymyr,Wright, Iain A.
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supporting information
(2020/02/13)
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- A vinylogous Michael addition-triggered quadruple cascade reaction for the enantioselective generation of multiple quaternary stereocenters
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An efficient organocatalytic quadruple cascade reaction resulting in spiroxindole scaffolds bearing five quaternary stereocenters is reported. The complex cascade reaction is triggered by the scarcely explored vinylogous Michael addition of 3-alkylidene o
- Yang, Shu-Mei,Karanam, Praneeth,Wang, Min,Jang, Yeong-Jiunn,Yeh, Yu-Sheng,Tseng, Ping-Yao,Ganapuram, Madhusudhan Reddy,Liou, Yan-Cheng,Lin, Wenwei
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supporting information
p. 1398 - 1401
(2019/02/05)
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- Visible light induced hydrodifluoromethylation of alkenes derived from oxindoles with (difluoromethyl)triphenylphosphonium bromide
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A visible light induced hydrodifluoromethylation of alkenes derived from oxindoles with (difluoromethyl)triphenylphosphonium bromide was developed. This reaction delivers a series of previously unknown difluoromethylated oxindoles containing C–CF2H quaternary centers in moderate to excellent yields. The resulting CF2H-containing oxindoles are potentially useful in drug discovery.
- Hu, Wei-Qiang,Xu, Xiu-Hua,Qing, Feng-Ling
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- Enantioselective Synthesis of Trifluoromethyl α,β-Unsaturated δ-Lactones via Vinylogous Aldol-Lactonization Cascade
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The novel vinylogous aldol-lactonization cascade of alkylidene oxindole with trifluoromethyl ketones is presented. The reaction, catalyzed by a bifunctional tertiary amine, provides an efficient application of the vinylogous reactivity of alkylidene oxindoles for the preparation of enantioenriched trifluoromethylated α,β-unsaturated δ-lactones.
- Crotti, Simone,Di Iorio, Nicola,Mazzanti, Andrea,Righi, Paolo,Bencivenni, Giorgio
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p. 12440 - 12448
(2018/10/09)
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- 1-chloroacetyloxindole(isatin) in reactions with some N-nucleophiles. Unexpetedly easy cleavage of chloroacetyl group
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Reactions of 1-chloroacetyloxindole and 1-chloroacetylisatin with some secondary amines, Girard’s reagent T and thiourea were studied. All investigated reactions proceeded via cleavage of the acyl group to form 3-substituted isatin or oxindole derivatives.
- Bogdanov,Kutuzova,Krivolapov,Dobrynin,Mironov
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p. 539 - 543
(2016/06/01)
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- Enantioselective photochemical rearrangements of spirooxindole epoxides catalyzed by a chiral bifunctional xanthone
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The title compounds were shown to undergo an enantioselective photochemical rearrangement to 3-acylindolin-2-ones (16-33% ee). A xanthone, which is tethered via an anellated oxazole to a chiral 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-one scaffold, efficiently catalyzed this reaction at 366nm, presumably by triplet sensitization. The observed enantioselectivity can be explained by hydrogen bonding of the oxindole substrate and the putative 1,3-diradical intermediate to the lactam part of the catalyst. Although one substrate enantiomer is processed with minor preference over the other, it was shown that the reaction is not stereospecific. Rather, the main reason for the observed selectivity is the enantioselective migration step.
- Maturi, Mark M.,P?thig, Alexander,Bach, Thorsten
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p. 1682 - 1692
(2015/11/17)
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- Regio- and diastereoselective vinylogous Mannich addition of 3-alkenyl-2-oxindoles to α-fluoroalkyl aldimines
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An efficient asymmetric vinylogous Mannich (AVM) addition reaction of 3-alkenyl-2-oxindoles to α-fluoroalkyl aldimines has been developed. This reaction provided various optical active α-alkylidene-δ-amino-δ-fluoroalkyl oxindoles in excellent yields, complete γ-site regioselectivity, and excellent diastereoselectivities.
- Liu, Yingle,Yang, Yi,Huang, Yangen,Xu, Xiu-Hua,Qing, Feng-Ling
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supporting information
p. 67 - 72
(2015/02/19)
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- An expedient synthesis of 3-alkylideneoxindoles by Ti(OiPr) 4/pyridine-mediated Knoevenagel condensation
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3-Alkylideneoxindoles have been prepared in excellent yields from oxindole and carbonyl compounds via an in situ generated titanium enolate of oxindole. (Z)-3-Alkylideneoxindoles could be synthesized selectively as major products from unsymmetrical ketones.
- Lee, Hyun Ju,Lim, Jin Woo,Yu, Jin,Kim, Jae Nyoung
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p. 1183 - 1187
(2014/02/14)
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- Phosphine-catalyzed enantioselective γ-addition of 3-substituted oxindoles to 2,3-butadienoates and 2-butynoates: Use of prochiral nucleophiles
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The first phosphine-catalyzed enantioselective γ-addition with prochiral nucleophiles and 2,3-butadienoates as the reaction partners has been developed. Both 3-alkyl- and 3-aryl-substituted oxindoles could be employed in this process, which is catalyzed by a chiral phosphine that is derived from an amino acid, thus affording oxindoles that bear an all-carbon quaternary center at the 3-position in high yields and excellent enantioselectivity. The synthetic value of these γ-addition products was demonstrated by the formal total synthesis of two natural products and by the preparation of biologically relevant molecules and structural scaffolds.
- Wang, Tianli,Yao, Weijun,Zhong, Fangrui,Pang, Guo Hao,Lu, Yixin
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supporting information
p. 2964 - 2968
(2014/04/03)
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- Reductive coupling of isatins with ketones and aldehydes by low-valent titanium
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The reductive coupling of isatins with ketones and aldehydes by Zn-TiCl4 in THF gave two- and four-electron reduced products, 3-hydoxy-3-(1-hydoxyalkyl)oxindoles and 3-alkylideneoxindoles, selectively by controlling the reaction conditions. Alt
- Kise, Naoki,Sasaki, Kouta,Sakurai, Toshihiko
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p. 9668 - 9675
(2015/01/08)
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- 3-alkenyl-2-silyloxyindoles: An enabling, yet understated progeny of vinylogous carbon nucleophiles
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We introduce novel 3-alkenyl-2-silyloxyindole nucleophiles and demonstrate their utility by developing an unprecedented vinylogous Mukaiyama-type aldol reaction with aromatic aldehydes. This reaction displays excellent levels of γ-site selectivity and dia
- Rassu, Gloria,Zambrano, Vincenzo,Tanca, Rossella,Sartori, Andrea,Battistini, Lucia,Zanardi, Franca,Curti, Claudio,Casiraghi, Giovanni
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supporting information; experimental part
p. 466 - 470
(2012/03/08)
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- A Facile Method for the Synthesis of 3-Alkyloxindole
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Benzylamine in combination with acetic acid was identified as a powerful catalyst for the condensation of oxindole with aldehydes, acetone or cyclic ketones. A variety of 3-alkyloxindoles could be readily prepared in 10 mmol scale via the sequential benzylamine acetate catalyzed condensation of oxindoles with aldehydes (or ketones) and conjugate reduction by NaBH4.
- Du, Tai-Ping,Zhu, Gang-Guo,Zhou, Jian
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experimental part
p. 225 - 232
(2012/07/14)
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- A comparison of the photosensitized rearrangement and the Lewis-acid-catalyzed rearrangement of spirooxindole epoxides
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Spirooxindole epoxides undergo smooth rearrangement either under photosensitization conditions or under Lewis acid catalysis to give different products. The photosensitized rearrangement of spirooxindole epoxides leads to 3-acyl-2-indolones, such as spiro
- Wang, Lihong,Su, Yibing,Xu, Xinmin,Zhang, Wei
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supporting information
p. 6606 - 6611
(2013/01/15)
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- CH activation and CH2 double activation of indolines by radical translocation: Understanding the chemistry of the indolinyl radical
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CH activation and CH2 double activation of indolines at C2 may be achieved efficiently through radical translocation. The fate of the C2 indolinyl radical is dictated by the substitution at C3. Fragmentation, cyclisation and tandem cyclisation reactions leading to indole, azaheterocycle and azapropellane formation, respectively, are reported. The Royal Society of Chemistry 2011.
- Harrowven, David C.,Stenning, Kerri J.,Whiting, Sally,Thompson, Toby,Walton, Robert
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supporting information; experimental part
p. 4882 - 4885
(2011/08/05)
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- Molybdenum-catalyzed asymmetric allylic alkylation of 3-alkyloxindoles: Reaction development and applications
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We report a full account of our work towards the development of Mo-catalyzed asymmetric allylic alkylation reactions with 3-alkyloxindoles as nucleophiles. The reaction is complementary to the Pd-catalyzed reaction with regard to the scope of oxindole nucleophiles. A number of 3-alkyloxindoles were alkylated successfully under mild conditions to give products with excellent yields and good-to-excellent enantioselectivities. Applications of this method to the preparation of indoline alkaloids such as (-)-physostigmine, ent-(-)-debromoflustramine B, and the indolinoquinoline rings of communesin B are reported.
- Trost, Barry M.,Zhang, Yong
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supporting information; experimental part
p. 2916 - 2922
(2011/05/02)
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- Seven 3-methyl-idene-1H-indol-2(3H)-ones related to the multiple-receptor tyrosine kinase inhibitor sunitinib
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The solid-state structures of a series of seven substituted 3-methyl-idene-1H-indol-2(3H)-one derivatives have been determined by single-crystal X-ray diffraction and are compared in detail. Six of the structures {(3Z)-3-(1H-pyrrol-2-ylmethyl-idene)-1H-in
- Spencer, John,Chowdhry, Babur Z.,Hamid, Samiyah,Mendham, Andrew P.,Male, Louise,Coles, Simon J.,Hursthouse, Michael B.
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experimental part
p. o71-o78
(2010/06/20)
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- Direct N-carbamoylation of 3-monosubstituted oxindoles with alkyl imidazole carboxylates
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(Chemical Equation Presented) Regioselective N-carbamoylation of oxindoles was achieved through the use of imidazole carboxylate reagents. This reaction provides ready access to N-carbamoyl-3-monosubstituted oxindoles.
- Trost, Barry M.,Zhang, Yong,Zhang, Ting
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supporting information; experimental part
p. 5115 - 5117
(2009/10/24)
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- Enantioselective construction of spirocyclic oxindolic cyclopentanes by palladium-catalyzed trimethylenemethane-[3+2]-cycloaddition
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The palladium catalyzed [3+2] trimethylenemethane (TMM) cycloaddition is an efficient method for the construction of cyclopentanes. Herein, we report a catalytic asymmetric protocol for the synthesis of spirocyclic oxindolic cyclopentanes in excellent yie
- Trost, Barry M.,Cramer, Nicolai,Silverman, Steven M.
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p. 12396 - 12397
(2008/09/16)
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- Novel N-substituted alpha aminoacid amides as calcium channel modulators
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The compounds of formula I and derivatives thereof have been found to be active in tests that show modulation of voltage-dependent calcium channels, and are thus indicated for use in the treatment of diseases in which such modulation is beneficial, in par
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- Studies in the Synthesis of Brevianamides A and B: Pilot Investigations and the Preparation of 1,1-Dimethyl-1,2,4,9-tetrahydrocarbazol-3-one
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In preliminary investigations directed ultimately at the synthesis of the indoxyl mould metabolites, brevianamides A and B, routes to the synthesis of 4,4-dimethyl-1,3,4,9-tetrahydrocarbazol-2-one and 1,1-dimethyl-1,2,4,9-tetrahydrocarbazol-3-one have bee
- Ritchie, Robert,Saxton, J. Edwin
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p. 528 - 545
(2007/10/02)
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- Photoinduced Cyclizations of Mono- and Dianions of N-Acyl-o-chloroanilines and N-Acyl-o-chlorobenzylamines as General Methods for the Synthesis of Oxindoles and 1,4-Dihydro-3(2H)-isoquinolinones
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Formation of the monoanions of a series of N-acyl-N-alkyl-o-chloroanilines by means of LDA in THF followed by irradiation with near-UV light affords 1,3-dialkyloxindoles in good yields.Similar photoinduced cyclizations of dianions derived from N-acyl-o-chloroanilines leads to 3-alkyloxindoles.Photocyclizations of mono- and dianion prepared from α,β-unsaturated o-haloanilides proceed to form 3-alkylideneoxindoles.Carbanions derived from N-acyl-o-chlorobenzylamines also undergo photoassisted ring closure to afford 1,4-dihydro-3(2H)-isoquinolinones.The influence of near-UV light and the effect of inhibitors implicate a radical-chain mechanism as the major reaction pathway in this convenient new method for oxindole and isoquinolinone synthesis.
- Goehring, R. Richard,Sachdeva, Yesh P.,Pisipati, Jyothi S.,Sleevi, Mark C.,Wolfe, James F.
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p. 435 - 443
(2007/10/02)
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- Reactions of 2-Hydroxytryptophol: Results of Strong Acid and Alkaline Treatments of 2-Hydroxytryptophol
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Upon being warmed at 90 deg C in trifluoromethanesulfonic acid for 42-78 h, 2-hydroxytriptophol (4a) gave 3-ethylideneoxidoles (E- and Z-form) (5a), while 3-methyl- (4b) or 3-ethyl-2-hydroxytryptophol (4c) gave the corresponding 3-alkylideneoxindoles (5b,
- Nozoye, Toshikazu,Shibanuma, Yoshihisa,Nakai, Tatsuya
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p. 2986 - 2992
(2007/10/02)
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