- Metal-free domino Cloke-Wilson rearrangement-hydration-dimerization of cyclopropane carbaldehydes: A facile access to oxybis(2-aryltetrahydrofuran) derivatives
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In this work, we have demonstrated a metal-free transformation of cyclopropane carbaldehydes to oxybis(2-aryltetrahydrofuran) derivatives via a domino Cloke-Wilson rearrangement-hydration-dimerization sequence. Commercially inexpensive p-toluene sulfonic acid (PTSA) was used as a Br?nsted acid catalyst, and reactions were conducted in an open-flask. Detection of reaction intermediates were carried to get an insight into the reaction pathway.
- Banerjee, Prabal,Dey, Raghunath,Rajput, Shruti
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- Regioselective Br?nsted Acid-Catalyzed Annulation of Cyclopropane Aldehydes with N′-Aryl Anthranil Hydrazides: Domino Construction of Tetrahydropyrrolo[1,2- a]quinazolin-5(1 H)ones
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A highly regioselective synthesis of tetrahydropyrrolo[1,2-a]quinazolin-5(1H)one derivatives was achieved by reacting cyclopropane aldehydes with N′-aryl anthranil hydrazides in the presence of p-toluene sulfonic acid (PTSA). The transformation involves domino imine formation and intramolecular cyclization to form 2-arylcyclopropyl-2,3-dihydroquinolin-4(1H)-one, followed by nucleophilic ring opening of the cyclopropyl ring to form desired tetrahydropyrrolo[1,2-a]quinazolin-5(1H)one in good to excellent yield with complete regioselectivity. This protocol tolerates a great variety of functional groups and thus provides a simple and step-efficient method for pyrroloquinazolinone synthesis.
- Banerjee, Prabal,Kaur, Navpreet,Singh, Priyanka
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p. 3393 - 3406
(2020/03/23)
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- Au Nanoparticle-Catalyzed Silaboration of Aryl-Substituted Cyclopropyl Aldehydes Forming Rearranged β-Boronate Silyl Enol Ethers
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2-Aryl-substituted cyclopropyl aldehydes undergo an unprecedented Au nanoparticle-catalyzed silaboration leading to rearranged linear β-boronate-bearing silyl enol ethers. Formation of these products is attributed to the ring opening radical clock rearran
- Kotzabasaki, Vasiliki,Kidonakis, Marios,Vassilikogiannaki, Eleni,Stratakis, Manolis
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supporting information
p. 7233 - 7236
(2019/11/19)
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- Synthesis of Photosensitive Cyclopropane-Containing Polymers
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New cyclopropyl methacrylate monomers were prepared, their radical polymerization was performed, and the composition and structure of the polymers obtained, containing reactive UV-sensitive fragments, were determined. Experiments on photochemical cross-li
- Guliyev,Rzayeva,Guliyev
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p. 1215 - 1222
(2019/11/03)
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- Metal-Free Ring Opening Cyclization of Cyclopropane Carbaldehydes and N-Benzyl Anilines: An Eco-Friendly Access to Functionalized Benzo[b]azepine Derivatives
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Herein, we report a p-toluenesulfonic acid (PTSA) initiated mild and user-friendly ring opening/domino ring opening cyclization reaction (depends on substituent present in N-benzyl aniline) of cyclopropane carbaldehyde and N-benzyl aniline towards the formation of substituted 4-amino butanal/2,3-dihydro-1H-benzo[b]azepine. The product dihydro-1H-benzo[b]azepine was also converted into the corresponding tetrahydro-1H-benzo[b]azepine. (Figure presented.).
- Dey, Raghunath,Banerjee, Prabal
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supporting information
p. 2849 - 2854
(2019/04/26)
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- Exploitation of Cyclopropane Carbaldehydes to Prins Cyclization: Quick Access to (E)-Hexahydrooxonine and Octahydrocyclopenta[ b]pyran
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A single-step TiX4-mediated Prins-type cyclization of cyclopropane carbaldehydes with 3-buten-1-ol for the highly stereoselective construction of relatively strained (E)-hexahydrooxonines is reported. Switching the alcohol to 3-butyn-1-ol prompted a similar route, augmented by another cyclization within a nine-membered ring to afford a bicyclized product (4,4-dihalo-5-aryloctahydrocyclopenta[b]pyran). Easy transformation of the resulting geminal dihalide to a vinyl halide and a ketone further supplemented the substance of this approach.
- Kumar, Pankaj,Dey, Raghunath,Banerjee, Prabal
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supporting information
p. 5163 - 5166
(2018/09/13)
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- Triazolopyridine ethers as potent, orally active mGlu2positive allosteric modulators for treating schizophrenia
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Triazolopyridine ethers with mGlu2positive allosteric modulator (PAM) activity are disclosed. The synthesis, in vitro activity, and metabolic stability data for a series of analogs is provided. The effort resulted in the discovery of a potent, selective, and brain penetrant lead molecule BMT-133218 ((+)-7m). After oral administration at 10 mg/kg, BMT-133218 demonstrated full reversal of PCP-stimulated locomotor activity and prevented MK-801-induced working memory deficits in separate mouse models. Also, reversal of impairments in executive function were observed in rat set-shifting studies at 3 and 10 mg/kg (p.o.). Extensive plasma protein binding as the result of high lipophilicity likely limited activity at lower doses. Optimized triazolopyridine ethers offer utility as mGlu2PAMs for the treatment of schizophrenia and merit further preclinical investigation.
- Higgins, Mendi A.,Marcin, Lawrence R.,Christopher Zusi,Gentles, Robert,Ding, Min,Pearce, Bradley C.,Easton, Amy,Kostich, Walter A.,Seager, Matthew A.,Bourin, Clotilde,Bristow, Linda J.,Johnson, Kim A.,Miller, Regina,Hogan, John,Whiterock, Valerie,Gulianello, Michael,Ferrante, Meredith,Huang, Yanling,Hendricson, Adam,Alt, Andrew,Macor, John E.,Bronson, Joanne J.
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p. 496 - 513
(2016/12/30)
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- Chiral recyclable fluorous disulfonamide ligand for catalytic enantioselective cyclopropanation of allylic alcohols
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Allylic alcohols reacted with Et2Zn and CH2I2 in the presence of a catalytic amount of fluorous disulfonamide 3a to afford the corresponding cyclopropylmethanols in 69%-quantitative yields with 49-85% ee. Recovery of the fluorous ligand 3a was readily performed from the reaction mixture by the fluorous solid-phase extraction (FSPE), and the recovered 3a could be reused without a significant loss of the catalytic activity and enantioselectivity.
- Kawashima, Yuya,Ezawa, Tetsuya,Yamamura, Mai,Harada, Taisuke,Noguchi, Takuya,Miura, Tsuyoshi,Imai, Nobuyuki
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p. 8585 - 8592
(2016/01/25)
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- TRIAZOLOPYRIDINE ETHER DERIVATIVES AND THEIR USE IN NEUROLOGICAL AND PYSCHIATRIC DISORDERS
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The disclosure generally relates to compounds of formula I, including their salts, as well as compositions and methods of using the compounds. The compounds modulate the mGluR2 receptor and may be useful for the treatment of various disorders of the central nervous system.
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Page/Page column 38-39
(2015/04/15)
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- Lewis Basic Sulfide Catalyzed Electrophilic Bromocyclization of Cyclopropylmethyl Amide
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A Lewis basic sulfide catalyzed electrophilic bromocyclization of cyclopropylmethyl amide has been developed. The catalytic protocol is applicable to both 1,1- and 1,2-substituted cyclopropylmethyl amides, giving oxazolines and oxazines in good yields and excellent diastereoselectivity.
- Wong, Ying-Chieh,Ke, Zhihai,Yeung, Ying-Yeung
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supporting information
p. 4944 - 4947
(2015/11/03)
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- Highly efficient asymmetric simmons-smith cyclopropanation promoted by chiral heteroorganic aziridinyl ligands
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Enantiomerically pure heteroorganic catalysts, bearing a hydroxy moiety, a stereogenic sulfinyl group, and a chiral aziridine moiety, have proved highly efficient in the asymmetric Simmons-Smith cyclopropanation of allylic alcohols, which generates the desired products in high yields (up to 95 %) and with ee values up to 94 %. The effect of the stereogenic centers at the sulfinyl sulfur atom and in the aziridine moiety on the stereochemical course of the title reaction is discussed. Combination at its best: Enantiomerically pure heteroorganic ligands, bearing a hydroxy moiety, a stereogenic sulfinyl group, and an enantiomeric aziridine moiety, have proved highly efficient in the asymmetric Simmons-Smith cyclopropanation of allylic alcohols, which generates the desired products in high yields (up to 95 %) and with ee values up to 94 %.
- Rachwalski, Michal,Kaczmarczyk, Sylwia,Lesniak, Stanislaw,Kielbasinski, Piotr
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p. 873 - 875
(2014/03/21)
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- Highly stereoselective Ru(ii)-Pheox catalyzed asymmetric cyclopropanation of terminal olefins with succinimidyl diazoacetate
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The Ru(ii)-Pheox complex is an efficient catalyst for the intermolecular cyclopropanation of various terminal olefins with succinimidyl diazoacetate. This catalytic system can perform under mild conditions, and the desired cyclopropane products are obtain
- Chanthamath, Soda,Phomkeona, Kesiny,Shibatomi, Kazutaka,Iwasa, Seiji
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supporting information; experimental part
p. 7750 - 7752
(2012/09/21)
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- A chiral bis(oxazoline) ligand embedded into polysiloxane gel: Application to a reusable copper catalyst for asymmetric cyclopropanation
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"Box"ed in: A novel polysiloxane gel encapsulated Cu II/bis(oxazoline) (CuII/Box) species was synthesized and used as a recyclable catalyst in the asymmetric cyclopropanation of alkenes with L-menthyl diazoacetate. Copyright
- Motoyama, Yukihiro,Nishikata, Takashi,Nagashima, Hideo
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supporting information; experimental part
p. 78 - 82
(2011/10/08)
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- Catalytic enantioselective cyclopropanation of allylic alcohols using recyclable fluorous disulfonamide ligand
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Cyclopropanation of allylic alcohols with Et2Zn and CH2I2 in the presence of a catalytic amount of fluorous disulfonamide 3 afforded the corresponding cyclopropylmethanols in 69-96% yield with 49-83% ee. The fluorous ligand 3 was readily recovered from the reaction mixture by the fluorous solid-phase extraction (FSPE) and could be reused without a significant loss of the catalytic activity and enantioselectivity.
- Miura, Tsuyoshi,Itoh, Keisuke,Yasaku, Yumi,Koyata, Naka,Murakami, Yasuoki,Imai, Nobuyuki
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p. 5813 - 5815
(2008/12/22)
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- Asymmetric Simmons-Smith reaction of allylic alcohols with Al Lewis acid/N Lewis base bifunctional Al(salalen) catalyst
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(Chemical Presented) Three angles: A highly enantioselective Simmons-Smith reaction of trans-disubstituted allylic alcohols was achieved by using a catalytic amount of an Al(salalen) complex at room temperature (see scheme).
- Shitama, Hiroaki,Katsuki, Tsutomu
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p. 2450 - 2453
(2008/12/23)
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- Preparation of highly optically active substituted 2,3-methanocinnamyl alcohols
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Cyclopropanation of a variety of substituted cinnamyl alcohols with Et2Zn and CH2I2 proceeded in the presence of a catalytic amount of (S)-2-(methanesulfonyl)amino-1-(p-toluenesulfonyl)amino-3-phenylpropane to afford the corresponding cyclopropylmethanols in excellent yields and with moderate to high enantioselectivity (51-86% ee). Highly enantiomerically enriched substituted 2,3-methanocinnamyl alcohols (84-97% ee) were obtained by conversion of the corresponding 2,3-methanocinnamyl alcohols produced in the enantioselective cyclopropanation to the 3,5-dinitrobenzoyl ester derivatives, followed by recrystallization and hydrolysis.
- Imai, Nobuyuki,Nomura, Tetsuro,Yamamoto, Shinya,Ninomiya, Yoshihiro,Nokami, Junzo
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p. 2433 - 2438
(2007/10/03)
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- Catalytic asymmetric cyclopropanation of allylic alcohols with titanium-TADDOLate: Scope of the cyclopropanation reaction
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A substoichiometric amount of titanium-TADDOLate complex was effective at catalyzing the cyclopropanation reaction of allylic alcohols in the presence 1 equiv of bis(iodomethyl) zinc. After initial optimization of the catalyst structure, excellent yields and enantiomeric ratios were obtained for 3-aryl- or 3-heteroaryl-substituted allylic alcohols (up to 97:3). Alkyl-substituted allylic alcohols gave modest yields and enantiomeric ratios (up to 87:13) but these compare favorably with those observed with other substoichiometric chiral ligands. The full synthetic scope of the reaction is presented in this paper.
- Charette,Molinaro,Brochu
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p. 12168 - 12175
(2007/10/03)
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- Highly Enantioselective Intermolecular Cyclopropanation Catalyzed by Dirhodium(II) Tetrakis[3(S)-phthalimido-2-piperidinonate]: Solvent Dependency of the Enantioselection
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The enantioselectivity in cyclopropanations catalyzed by dirhodium(II) tetrakis[3(S)-phthalimido-2-piperidinonate] has been found to be substantially improved by employing ether as the rarely used solvent. Cyclopropanations of styrenes or 1,1-disubstituted alkenes with 2,4-dimethyl-3-pentyl diazoacetate in ether are promoted by this catalyst to afford the corresponding cyclopropane products in the highest levels of enantioselectivity (up to 98% ee) reported to date for the dirhodium(II)-catalyzed intermolecular cyclopropanation reactions.
- Kitagaki, Shinji,Matsuda, Hideo,Watanabe, Nobuhide,Hashimoto, Shun-Ichi
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p. 1171 - 1174
(2007/10/03)
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- N,N,N′,N′-Tetraalkyl-2,2′-dihydroxy-1,1′- binaphthyl-3,3′-dicarboxamides: Novel Chiral Auxiliaries for Asymmetric Simons-Smith Cyclopropanation of Allylic Alcohols and for Asymmetric Diethylzinc Addition to Aldehydes
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The newly introduced tittle compounds were found to be efficient chiral auxiliaries for the asymmetric Simmons-Smith cyclopropanation of allylic alcohols and for asymmetric addition of diethylzinc to aldehydes. For example, Simmons- Smith cyclopropanation of cinnamyl alcohol in the presence of N,N,N′,N′-tetraethyl-2,2′-dihydroxy-1, 1′-binaphthyl-3, 3′-dicarboxamide (1b) proceeded with high enantioselectivity of 94% ee and addition of diethylzinc to benzaldehyde in the presence of N,N,N′,N′-tetraisopropyl-2,2′-dihydroxy-1,1′-binaphthyl- 3,3′-dicarboxamide (1e) proceeded with enantioselectivity of 99% ee. Although the reaction mechanism of these reactions is still nuclear, a monomeric seven-membered 2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxamide (1)-Zn complex is considered to be an active species which catalyzes the above reactions, on the basis of NMR experiments.
- Kitajima, Hiroshi,Ito, Katsuji,Aoki, Yuko,Katsuki, Tsutomu
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p. 207 - 217
(2007/10/03)
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- Transmission of Electronic Effects through 2--1--Cyclopropane
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The through-ring conjugation between ?-donor and attractor substituents on vicinal carbons of cyclopropane with the direct participation of the ring was assessed using proton and 13C NMR.Appropriate 1H NMR correlations were obtained between ?p and δH of the trimethylene protons.However, aryl through-space field effects were found to obscure individual conjugative effects.Conversely, the 13C NMR data implied the occurrence of competitive conjugation of ?-groups with the ring but gave no proof for the existence of the actual transmission of conjugative effects through the C-1-C-2 bond of the ring.
- Alonso, Miguel E.,Pekerar, Sarah V.,Borgo, Maria L.
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p. 956 - 962
(2007/10/02)
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