- Triaryl methane derivatives as antiproliferative agents
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Clotrimazole (CLT) 1, a synthetic anti-fungal imidazole derivative, inhibits tumor cell proliferation and angiogenesis. In the current study, flow cytometric analysis demonstrated that the decrease in tumor cell growth by CLT 1 was associated with inhibition of cell cycle progression at the G 1-S phase transition, resulting in G0-G1 arrest. A series of CLT 1 analogues has been generated in order to develop CLT 1 derivatives that are devoid of the imidazole moiety which is responsible for the hepatoxicity associated with CLT 1 while retaining CLT 1 efficacy. The majority of these analogues demonstrate in vitro antiproliferative activity ranging from submicromolar to micromolar concentrations.
- Al-Qawasmeh, Raed A.,Lee, Yoon,Cao, Ming-Yu,Gu, Xiaoping,Vassilakos, Aikaterini,Wright, Jim A.,Young, Aiping
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- Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes
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An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.
- Chen, Xing,Li, Mengke,Liu, Zhipeng,Yang, Can,Xie, Haisheng,Hu, Xinwei,Su, Shi-Jian,Jiang, Huanfeng,Zeng, Wei
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supporting information
p. 6724 - 6728
(2021/09/08)
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- Gold-catalyzed tandem annulations of pyridylhomopropargylic alcohols with propargyl alcohols
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A gold-catalyzed tandem annulation of propargylic alcohols and pyridylhomopropargylic alcohols is achieved, providing an atom-economical approach to a diverse set of polycyclic dihydrobenzofurans in good yields. The reaction proceeds via the 5-endo-dig cyclization/Meyer?Schuster rearrangement/Friedel?Crafts-type pathway. In this way, three C?C bonds and one C? O bond form to give a polycyclic skeleton in a one-pot process. Moreover, the products exhibit unique optical properties, which reveal their potential application value.
- Li, Xue-Song,Xu, Dan-Tong,Niu, Zhi-Jie,Li, Ming,Shi, Wei-Yu,Wang, Cui-Tian,Wei, Wan-Xu,Liang, Yong-Min
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supporting information
p. 832 - 836
(2021/02/16)
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- Calcium-Catalyzed Intramolecular Hydroamination-Deacylation Reaction of in situ formed β-Amino Allenes
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We have developed a simple, One-Pot, three-component reaction of tert-propargyl alcohols, primary amines and acyl ketones to synthesize fully substituted pyrroles and pyridine derivatives in good to excellent yields with large substrate diversity. An eco-friendly calcium catalyst catalyzes the reaction to form the key intermediate β-amino allene that undergoes subsequent Thorpe-Ingold effect assisted hydroamination and aromaticity driven deacylation reaction to yield fully substituted five and six-membered azacyclic compounds. (Figure presented.).
- Yaragorla, Srinivasarao,Latha, Dandugula Sneha,Rajesh, Pallava
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supporting information
p. 5486 - 5492
(2021/12/10)
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- Lewis-Acid-Catalyzed Tandem Cyclization by Ring Expansion of Tertiary Cycloalkanols with Propargyl Alcohols
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A new method for the efficient synthesis of hexahydro-1H-fluorene and octahydrobenzo[a]azulene derivatives through a ring-expansion strategy is reported. With an appropriate combination of thulium(III) trifluoromethanesulfonate and 13X molecular sieves, a range of unsaturated polycyclic compounds were obtained in good yields. Mechanism studies reveal that the reaction is more likely to undergo Meyer–Schuster rearrangement, ring expansion, and Friedel–Crafts-type pathways, which provide a conceptually different strategy for the ring opening of tertiary cycloalkanols.
- Kong, Xiangtao,Li, Xue-Song,Li, Yuke,Liang, Yong-Min,Liu, Hong-Chao,Niu, Zhi-Jie,Wang, Cui-Tian,Wei, Wan-Xu,Zhang, Zhe
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supporting information
p. 9457 - 9462
(2021/12/14)
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- Synthesis of 1H-Pyrrolo[1,2-a]indoles via Lewis Acid-Catalyzed Annulation of Propargylic Alcohols with 2-Ethynylanilines
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A novel highly efficient, environmentally benign Lewis acid-catalyzed, and protection-free protocol for the construction of valuable polycyclic products bearing a 1H-pyrrolo[1,2-a]indole scaffold is described, starting from readily available propargylic alcohols and 2-ethynylanilines. The one-pot transformation entails the cleavage of one C?O bond, and the construction of two C?N bonds and one C?C double bond. This unique operationally simple method is performed under mild conditions and in air, producing water as the only byproduct; it is scalable and demonstrates good functional group compatibility and broad scope.
- Du, Li-Juan,Han, Ya-Ping,Liang, Yong-Min,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
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supporting information
(2020/03/04)
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- Br?nsted Acid Promoted Thermal-Ring-Rearrangement of Fluorenopyrans to 2-(1H-Inden-3-yl)-9H-fluoren-3-ols Bearing Two All-Carbon-Quaternary Centres
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4-Aryl-fluorenopyrans bearing quaternary centre at C2 and C6 positions underwent a thermal-ring-rearrangement with a catalytic amount of pTsOH to furnish 2-(1H-inden-3-yl)-9H-fluoren-3-ols with two all carbon-quaternary centres, in which one is retained a
- Jose, K. V. Jovan,Khan, Tabassum,Praveen, Dudam,Rajesh, P.,Yaragorla, Srinivasarao
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supporting information
(2020/04/22)
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- In Situ Generation of Allenes and their Application to One-Pot Assembly of Functionalized Fluoreno[3,2-b]furans by Calcium-Catalyzed, Regioselective, 3-Component Reactions
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We have developed a novel synthetic methodology for the preparation of tetra-annulated fluorenofurans and fluorenopyrans using calcium(II)-catalyzed one-pot, three-component reaction. In this reaction, tert-propargyl alcohols react with 1,3-dicarbonyls to form tetra-substituted allenes, which are subsequently undergoing regiodivergent annulation with sec-propargyl alcohols to produce the fluorene-fused furan compounds. Broad substrate scope, regioselectivity, gram-scale synthesis, and benzylic functionalization of products are some of the highlights of this protocol.
- Rajesh, Pallava,Yaragorla, Srinivasarao
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supporting information
p. 7243 - 7251
(2020/12/01)
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- Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-Schuster rearrangement/conjugate addition reaction
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A new strategy to prepare acyclic β-carbonyl thioethers from propargyl alcohols and sulfur nucleophiles is reported. The investigation of the reaction substrates scope indicated that primary 3-aryl propargyl alcohols and thiols underwent the transformation smoothly. The reaction probably proceeded a Bi(OTf)3-catalyzed tandem Meyer-Schuster rearrangement of 3-aryl propargyl alcohol, followed by a thiol Michael conjugate addition of thiols to in situ generated α, β-unsaturated ketones. The method was 100% atom economic, high-yielding, and easy to handle, making it a valuable method for the construction of β-carbonyl sulfides.
- Wang, Yuan,Yin, Yan,Zhang, Qinglin,Pan, Wanyong,Guo, Huifeng,Pei, Keke
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supporting information
p. 2030 - 2034
(2019/07/03)
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- Regiospecific formal [3 + 2] annulation of: Tert -propargyl alcohols with acyclic 1,3-diketones via the cycloisomerization of homoallenyl ketones
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A one-pot, regiospecific synthesis of dihydrofurans bearing a quaternary centre and tetrasubstituted furans is developed from the formal [3 + 2] annulation of tert-propargyl alcohols and 1,3-diketones under Ca(ii)/DBU conditions. The reaction proceeds through the SN2I mechanism to form homoallenyl ketone and a subsequent cycloisomerization to yield novel and new chemical entities of privileged scaffolds.
- Yaragorla, Srinivasarao,Rajesh
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supporting information
p. 1924 - 1928
(2019/02/20)
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- An efficient Benzannulation protocol for the synthesis of 9,9-Diphenyl-9H-fluorenols using Intramolecular Allene Friedel–Crafts Annulation
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Herein we report a one-pot cascade benzannulation protocol for the synthesis 9,9-diaryl-9H-fluorenol, a key structure of many important natural products which exhibit the significant biological activities particularly phosphodiesterase-4 (PDE4) inhibitory activity. This approach proceeds through the annulation of tert-propargyl alcohols with 2-methyl acetylacetone through an intramolecular allene Friedel–Crafts reaction using Ca(OTf)2 as the environmentally benign catalyst. Synthetic transformations of these compounds to useful materials are also presented here with the aid of cross-coupling and RCM reactions.
- Yaragorla, Srinivasarao,Rajesh
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supporting information
p. 5740 - 5748
(2019/08/20)
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- Ca(II)-Mediated Regioselective One-pot Sequential Annulation of Acyclic compounds to Polycyclic Fluorenopyrans
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Herein we report a facile synthesis of tetracyclic fluorenopyrans from simple acyclic reactants, propargyl alcohols and 3-methylpentane-2,4-dione under calcium catalysis. This one-pot, 3-component reaction proceeds through a sequential allene formation, F
- Yaragorla, Srinivasarao,Rajesh,Pareek, Abhishek,Kumar, Ankit
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supporting information
p. 4422 - 4428
(2018/10/20)
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- Br?nsted Acid-Mediated Formal [3+3] Annulation Between Propargylic Alcohols and 1,3-Diketones
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A Br?nsted acid-mediated formal [3+3] cascade annulation of propargylic alcohols with 1,3-diketones proceeds through a sequential Meyer?Schuster rearrangement/1,2-addition. This protocol, which has a wide scope and is conducted under an ambient atmosphere
- Han, Ya-Ping,Li, Xue-Song,Zhu, Xin-Yu,Sun, Zhou,Li, Ming,Wang, Yu-Zhao,Liang, Yong-Min
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supporting information
p. 870 - 874
(2017/12/26)
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- Lewis Acid-Catalyzed Formal [3+3] Annulation of Propargylic Alcohols with 4-Hydroxy-2H-chromen-2-ones
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A Lewis acid-catalyzed formal [3+3] cascade annulation strategy for the formation of diverse tricyclic compounds possessing functionalized pyrano[3,2-c]chromen-5(2H)-one fragments has been developed using propargylic alcohols and 4-hydroxy-2H-chromen-2-on
- Han, Ya-Ping,Li, Xue-Song,Li, Ming,Zhu, Xin-Yu,Liang, Yong-Min
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supporting information
p. 2796 - 2800
(2018/08/17)
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- Lewis Acid-Catalyzed Annulation of Propargylic Alcohols with (Z)-2-Styryl-1H-Indoles
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A novel copper(II) trifluoromethanesulfonate-catalyzed intermolecular cascade annulation strategy for the construction of a great variety of pentacyclic compounds possessing valuable carbazole fragments was developed employing propargylic alcohols and (Z)-2-styryl-1H-indoles as the initial substrates. This protocol, which entails a sequential Meyer-Schuster rearrangement/isomerization/-cyclization cascade, enables facile and atom-economical access to various pentacyclic compounds with broad functional-group tolerance in good yields under mild conditions. The conversion could be efficiently scaled up to gram quantities, accentuating a potential application of this work. (Figure presented.).
- Li, Xue-Song,Han, Ya-Ping,Zhu, Xin-Yu,Xia, Yu,Wei, Wan-Xu,Li, Ming,Liang, Yong-Min
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supporting information
p. 4441 - 4445
(2018/10/15)
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- Transition-Metal-Free, Br?nsted Acid-Mediated Cascade Sequence in the Reaction of Propargyl Alcohols with Sulfonamido-indoles/-indolines: Highly Substituted δ- And α-Carbolines
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Br?nsted acid-mediated, transition-metal-free reaction of propargyl alcohols with sulfonamido-indoles/-indolines under mild conditions affords highly substituted δ- or α-carbolines in good to excellent yields. This protocol involves cascade reaction seque
- Selvaraj, Karuppu,Swamy, K. C. Kumara
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supporting information
p. 15043 - 15056
(2019/01/04)
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- On the Distribution of Linear versus Angular Naphthalenes in Aromatic Tetradehydro-Diels–Alder Reactions – Effect of Linker Structure and Steric Bulk
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We report here a systematic study of the aromatic tetradehydro-Diels–Alder (Ar-TDDA) reaction to elucidate the factors that have significant effects on the distribution of linear and angular naphthalene products. Two factors were studied, that is, the nat
- Chinta, Bhavani Shankar,Baire, Beeraiah
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supporting information
p. 3381 - 3385
(2017/06/29)
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- Tert-butoxy rare earth/sodium impurity bimetallic complex, as well as preparation method and use thereof
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The invention discloses a tert-butoxy rare earth/sodium hetero-bimetallic complex as well as a preparation method and use thereof. The molecular formula of the tert-butoxy rare earth/sodium hetero-bimetallic complex is LnNa8[OC(CH3)3]10(OH), and Ln repres
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Paragraph 0056-0057
(2017/07/13)
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- Cobalt-Catalyzed Asymmetric Hydroboration/Cyclization of 1,6-Enynes with Pinacolborane
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We report a cobalt-catalyzed asymmetric hydroboration/cyclization of 1,6-enynes with catalysts generated from Co(acac)2 and chiral bisphosphine ligands and activated in situ by reaction with pinacolborane (HBpin). A variety of oxygen-, nitrogen
- Yu, Songjie,Wu, Caizhi,Ge, Shaozhong
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supporting information
p. 6526 - 6529
(2017/05/29)
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- Lewis Acid-Catalyzed [4+2] Annulation between Propargylic Alcohols with Benzo[d]isoxazoles
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An unprecedented copper(II) trifluoromethanesulfonate-catalyzed [4+2] cascade annulation of propargylic alcohols with benzo[d]isoxazoles proceeds through a sequential ring opening/Meyer–Schuster rearrangement/intermolecular cyclization. This protocol, whi
- Han, Ya-Ping,Li, Xue-Song,Sun, Zhou,Zhu, Xin-Yu,Li, Ming,Song, Xian-Rong,Liang, Yong-Min
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supporting information
p. 2735 - 2740
(2017/08/23)
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- Regioselective annulation of propargyl alcohols with ambident-enols: A Ca(II)-catalyzed trisubstituted benzochromene synthesis
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Highly regioselective, 6-endo cyclization between propargyl alcohols and ambident enols such as naphthols, 4-hydroxy coumarin, cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione is described using Ca(OTf)2 under solvent free conditions. The reaction proceeds through a cascade annulation which involves an etherification, Claisen type rearrangement, allene formation and endocyclization. Further, we extended this method to the synthesis of iodo-derivative and demonstrated the reactivity in cross-coupling reactions.
- Yaragorla, Srinivasarao,Pareek, Abhishek,Dada, Ravikrishna
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supporting information
p. 4642 - 4647
(2017/11/15)
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- Lewis Acid Catalyzed Cyclization of Propargylic Alcohols with 2-Vinylphenol
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An unprecedented Lewis acid catalyzed, protection-free, and high-efficiency synthesis of valuable 3,4-dihydro-2H-2,4-methanochromans via cycloaddition of propargylic alkynols with 2-vinylphenol is described. This cycloaddition protocol, which tolerates a
- Han, Ya-Ping,Song, Xian-Rong,Qiu, Yi-Feng,Li, Xue-Song,Zhang, Heng-Rui,Zhu, Xin-Yu,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information
p. 3866 - 3869
(2016/08/16)
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- Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
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A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.
- Martinez-Erro, Samuel,Sanz-Marco, Amparo,Bermejo Gómez, Antonio,Vázquez-Romero, Ana,Ahlquist, M?rten S. G.,Martín-Matute, Belén
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supporting information
p. 13408 - 13414
(2016/10/22)
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- Convenient synthesis of naphthopyrans using montmorillonite K-10 as heterogeneous catalyst
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A simple and mild procedure for the synthesis of different naphthopyrans providing high yields in a short reaction time was reported. The reaction of propargylic alcohols with α- or β-naphthol and dihydroxy naphthalenes in the presence of montmorillonite K-10 was studied. This reaction afforded high yields of the corresponding naphthopyrans. In addition, a number of new phenylene and biphenylen-linked bisnaphthopyrans were synthesized providing excellent yields via the one-pot reaction of bis-propargyl alcohols with β-naphthol.
- Hosseinzadeh, Rahman,Mohadjerani, Maryam,Javad Ardestanian, Mohammad,Naimi-Jamal, Mohammad Reza,Lasemi, Zahra
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p. 1081 - 1089
(2014/11/08)
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- TMSCl-mediated synthesis of α,β-unsaturated amides via C-C bond cleavage and C-N bond formation of propargyl alcohols with trimethylsilyl azide
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A new method with high efficiency for the synthesis of α,β- unsaturated amides from the easily prepared propargyl alcohols and TMSN 3 using TMSCl as an acid promoter is developed. A wide variety of α,β-unsaturated amides were produced in moderate to excellent yields. Mechanistic studies indicate that this transformation involves TMSCl-mediated allenylazide intermediate formation, C-C bond cleavage, and C-N bond formation. Significantly, this reaction shows good functional group compatibility and high regioselectivity, with a relatively short reaction time and inexpensive reagents.
- Song, Xian-Rong,Song, Bo,Qiu, Yi-Feng,Han, Ya-Ping,Qiu, Zi-Hang,Hao, Xin-Hua,Liu, Xue-Yuan,Liang, Yong-Min
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p. 7616 - 7625
(2014/09/16)
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- Lewis acid mediated tandem reaction of propargylic alcohols to tetrazoles involving C-O- and C-C-bond cleavage reactions and a C-N-bond formation
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A novel and direct synthesis of 1-aryl-5-arylvinyl-tetrazoles from easily prepared propargylic alcohols and TMSN3 is developed in the presence of TMSCl under mild conditions (TMS=trimethylsilyl). The process involves an allenylazide intermediate, followed by a C-C-bond cleavage and C-N-bond formation to afford the desired products. Moreover, this method offers a good functional-group applicability and can be scaled-up to grams (yield up to 85%).
- Song, Xian-Rong,Han, Ya-Ping,Qiu, Yi-Feng,Qiu, Zi-Hang,Liu, Xue-Yuan,Xu, Peng-Fei,Liang, Yong-Min
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supporting information
p. 12046 - 12050
(2015/03/31)
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- Br?nsted acid-catalyzed meyer-schuster rearrangement for the synthesis of α, β -unsaturated carbonyl compounds
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An efficient and simple protocol for the Meyer-Schuster rearrangement of propargyl alcohols into α,β-unsaturated carbonyl compounds has been developed using catalytic amounts of p-toluenesulfonic acid in 1,2-dichloroethane.
- Park, Jungmin,Yun, Jihee,Kim, Jaehyun,Jang, Dong-Jin,Park, Cheol Ho,Lee, Kooyeon
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supporting information
p. 1924 - 1929
(2014/07/07)
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- Regioselective rapid synthesis of fully substituted 1,2,3-triazoles mediated by propargyl cations
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Regioselective rapid triazole syntheses at low temperature are described. Organic azides and propargyl cations generated by acids gave fully substituted 1H-1,2,3-triazoles. Most reactions could be performed in 5 min at not only rt but also -90 C. Both terminal and internal alkynes were acceptable, and the sterically bulky substituents could afford the products smoothly. Various types of three-component coupling reactions were demonstrated, and the presence of allenylaminodiazonium intermediates was indicated.
- Zhang, Huan,Tanimoto, Hiroki,Morimoto, Tsumoru,Nishiyama, Yasuhiro,Kakiuchi, Kiyomi
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supporting information
p. 5222 - 5225
(2013/11/06)
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- Efficient solvent-free synthesis of tertiary propargylic alcohols from arylacetylenes and ketones promoted by tert-BuOK
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A mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols. Graphical abstract: A mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols.[Figure not available: see fulltext.]
- Chen, Shufeng,Yuan, Fang,Zhao, Haiying,Li, Baoguo
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p. 2391 - 2399
(2013/07/26)
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- Doing the methylene shuffle - Further insights into the inhibition of mitotic kinesin Eg5 with S-trityl l-cysteine
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S-Trityl l-cysteine (STLC) is an inhibitor of the mitotic kinesin Eg5 with potential as an antimitotic chemotherapeutic agent. We previously reported the crystal structure of the ligand-protein complex, and now for the first time, have quantified the interactions using a molecular dynamics based approach. Based on these data, we have explored the SAR of the trityl head group using the methylene shuffle strategy to expand the occupation of one of the hydrophobic pockets. The most potent compounds exhibit strong (100 nM) inhibition of Eg5 in the basal ATPase assay and inhibit growth in a variety of tumour-derived cell lines.
- Abualhasan, Murad N.,Good, James A.D.,Wittayanarakul, Kitiyaporn,Anthony, Nahoum G.,Berretta, Giacomo,Rath, Oliver,Kozielski, Frank,Sutcliffe, Oliver B.,MacKay, Simon P.
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experimental part
p. 483 - 498
(2012/09/10)
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- Synthesis of 2,3-diiodoindenes and their applications in construction of 13H-indeno[1,2-l]phenanthrenes
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A series of 2,3-diiodoindene were synthesized at first, and 13H-indeno[1,2-l]phenanthrenes were then constructed via a Suzuki coupling reaction and subsequently a Scholl reaction. Structures of synthesized compounds were fully characterized by 1H NMR, 13C NMR, and HRMS. Their photophysical properties, such as UV-vis and FL spectra were investigated, and electronic properties were theoretically calculated by the software of Gaussian 03. The results suggested that these modified indene and indenophenanthrene compounds might have potential applications as light emitting materials.
- Zhou, Chao,Chen, Xiaopeng,Lu, Ping,Wang, Yanguang
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supporting information; experimental part
p. 2844 - 2850
(2012/05/05)
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- Efficient catalytic transition-metal-free conditions for nucleophilic addition of arylacetylenes to aromatic ketones
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A mild, efficient, and transition-metal-free method for nucleophilic addition of arylacetylenes to diverse aromatic ketones, using catalytic amount of tetrabutylammonium chloride as a promoter and solid KOH as a base in THF, was developed to afford aromat
- Liu, Junfeng,Lin, Jin,Song, Ling
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supporting information; experimental part
p. 2160 - 2163
(2012/05/05)
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- One-pot consecutive reactions based on the synthesis of conjugated enones by the re-catalysed meyer-schuster rearrangement
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Re catalysis in one-pot reactions: An atom-economical, one-pot strategy that involves alkyne deprotonation and a subsequent rhenium(V)-catalysed Meyer-Schuster rearrangement of the alkynol to provide α,β- unsaturated enones in high yield has been developed (see scheme). Subsequent in situ hydride reduction or Diels-Alder reaction of the enones provided products in good-to-high overall yields. Copyright
- Mattia, Elio,Porta, Alessio,Merlini, Valentina,Zanoni, Giuseppe,Vidari, Giovanni
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supporting information
p. 11894 - 11898
(2012/10/29)
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- The rubrenic synthesis: The delicate equilibrium between tetracene and cyclobutene
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Herein we describe the synthesis of new substituted tetraaryltetracenes, obtained by the dimerization of triarylchloroallenes, prepared from propargyl alcohols. The propargyl alcohols were prepared by two different synthetic strategies and then the alcohols were treated to obtain the corresponding acenes. In addition to the expected tetracene derivatives, we observed the formation of bis(alkylidene)cyclobutenes. When strong electron-donating substituents were present, the main product was the cyclobutene. We discuss a reaction mechanism that accounts for the formation of the cyclobutenes.
- Braga, Daniele,Jaafari, Abdelhafid,Miozzo, Luciano,Moret, Massimo,Rizzato, Silvia,Papagni, Antonio,Yassar, Abderrahim
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experimental part
p. 4160 - 4169
(2011/10/01)
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- Efficient synthesis of di- and trisubstituted 2-aryloxazoles via ytterbium(III) triflate catalyzed cyclization of tertiary propargylic alcohols with aryl amides
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An efficient synthetic method to prepare di- and trisubstituted 2-aryloxazoles based on Yb(OTf)3 catalyzed cyclization of trisubstituted propargylic alcohols with aryl amides is described. The reaction was accomplished in moderate to excellent product yields and with complete regioselective control. The mechanism is suggested to involve activation of the starting alcohol by the metal catalyst that results in its ionization. Subsequent cyclization of this newly generated carbocationic species with the aryl amide then affords the oxazole. In view of the mild conditions along with the low cost, commercially availability of Yb(OTf)3 and its high tolerance to air and moisture, the present synthetic approach offers an operationally simplistic and convenient route to this important aromatic heterocycle.
- Zhang, Xiaoxiang,Teo, Wan Teng,Chan, Philip Wai Hong
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supporting information; experimental part
p. 331 - 337
(2011/02/17)
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- Tandem reaction of propargyl alcohol and N-sulfonylhydrazone: Synthesis of dihydropyrazole and its utility in the preparation of 3,3-diarylacrylonitrile
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An efficient and straightforward strategy for the synthesis of 4-methylene-1-(phenylsulfonyl)-4,5-dihydro-1H-pyrazole from propargyl alcohol and N-sulfonylhydrazone is described. N-Sulfonyl allenamide is postulated to be the key intermediate for this tandem transformation.
- Zhu, Yuanxun,Wen, Shan,Yin, Guangwei,Hong, Deng,Lu, Ping,Wang, Yanguang
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supporting information; experimental part
p. 3553 - 3555
(2011/09/14)
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- Unexpected iron(iii) chloride-catalysed dimerisation of 1,1,3-trisubstituted-prop-2-yn-1-ols as an expedient route to highly conjugated indenes
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A method to prepare highly conjugated indenes efficiently by iron(iii) chloride-catalysed dimerisation of trisubstituted propargylic alcohols under very mild conditions at room temperature is described. The reactions are rapid and operationally straightfo
- Rao, Weidong,Chan, Philip Wai Hong
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supporting information; experimental part
p. 4016 - 4025
(2010/09/17)
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- Bronsted acid catalyzed cyclization of propargylic alcohols with thioamides. Facile synthesis of Di- and trisubstituted thiazoles
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Figure presented. A general and efficient method to prepare 2,4-di- and trisubstituted thiazoles via p-TsOH·H2O-catalyzed cyclization of trisubstituted propargylic alcohols with thioamides is described. The reaction was accomplished in moderate to excellent product yields under mild conditions that did not require the exclusion of air and moisture and offers an operationally simplistic and convenient route to this synthetically useful aromatic heterocycle.
- Zhang, Xiaoxiang,Teo, Wan Teng,Sally,Chan, Philip Wai Hong
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supporting information; experimental part
p. 6290 - 6293
(2010/11/18)
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- Ytterbium(III) triflate catalyzed tandem friedel-crafts alkylation/hydroarylation of propargylic alcohols with phenols as an expedient route to indenols
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A method to prepare indenols efficiently by ytterbium(III) triflate catalyzed tandem Friedel - Crafts alkylation/hydroarylation of propargylic alcohols with phenols is described. The reaction was accomplished In moderate to excellent yields and regioselectivity under mild conditions and offers a straightforward and convenient one step synthetic route to bioactive indenols and its derivatives.
- Zhang, Xiaoxiang,Teo, Wan Teng,Chan, Philip Wai Hong
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supporting information; experimental part
p. 4990 - 4993
(2009/12/28)
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- Unprecedented consecutive, competitive nucleophilic addition to construct densely functionalized propargylic alcohols
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An efficient one-pot process to construct a series of polyfunctionalized propargylic alcohol derivatives from the simple materials without functional protection was investigated. A solution of nBuLi in hexane was added into dry THF by syringe the resulting solution was then maintained at RT for 3 hours. the freshly prepared lithium enolate of acetaldehyde was used directly in the reaction. The nBuLi was added over a period of 30 minutes by syringe to a solution of terminal alkyne in THF at -30°C. The scope and limitations of the reaction was explored by examining other terminal alkynes. A number of different carbonyl-containing substrates were also examined. It was observed that propargylic alcohol derivatives are important synthetic intermediates in organic synthesis.
- Liu, Jie,An, Yan,Wang, Ya-Hui,Jiang, Hai-Ying,Zhang, Yu-Xin,Chen, Zili
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supporting information; experimental part
p. 9131 - 9134
(2009/09/06)
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- Synthesis of propargylic alcohols by base promoted alkynylation of ketones with ethynylbenzene using ionic liquid [(bmim) PF6]
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A mild and efficient addition of ethynylbenzene with ketones using KOH in ionic liquid 1-butyl-3-methylimidazolium hexaflurophosphate [(bmim) PF 6] gives propargylic alcohols in high yields.
- Jagtap, Sachin R.,Bhanage, Bhalchandra M.
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p. 370 - 372
(2008/09/16)
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- Metal-free catalytic nucleophilic substitution of propargylic alcohols
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Organic acids such as PTS efficiently catalyze direct nucleophilic substitutions of the hydroxy groups of propargylic alcohols with a large variety of carbon- and heteroatom-centered nucleophiles. Reactions can be conducted under mild conditions and in air without the need for dried solvents. Reactions on multigram scales are also possible. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Sanz, Roberto,Martinez, Alberto,Alvarez-Gutierrez, Julia M.,Rodriguez, Felix
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p. 1383 - 1386
(2007/10/03)
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- Olefination of ketones using a gold(III)-catalyzed Meyer-Schuster rearrangement
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An atom-economical and efficient olefination strategy for ketones is described. Ethoxyacetylide addition followed by a gold-catalyzed Meyer-Schuster rearrangement affords α,β-unsaturated esters, generally in excellent overall yield from the starting ketones. The alkynophilicity of Au3+ promotes an interaction with the electron-rich acetylenes that catalyzes the Meyer-Schuster rearrangement selectively over other conceivable pathways.
- Engel, Douglas A.,Dudley, Gregory B.
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p. 4027 - 4029
(2007/10/03)
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- Synthesis of tetraarylallenes via palladium-catalyzed addition-elimination reactions of 1,1,3-triaryl-2-propyn-1-ols with aryl iodides
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The palladium-catalyzed reactions of tert-propargylic alcohols with aryl iodides afforded tetraarylallenes in good yields. This reaction involves: (1) oxidative addition of the aryl iodide to Pd(O); (2) arylpalladium intermediate coordination to the carbon-carbon triple bond of the 1,1,3-triaryl-2-propyn-1-ol and subsequent regioselective insertion of the alkynol to form β-hydroxyvinylpalladium species; and (3) β-elimination to produce the tetraarylallenes. Generally, the best results are obtained by employing 5 mol% of Pd(TFA)2, 10 mol% of PPh3, two equivalents of aryl iodide and five equivalents of Et3N in MeCN. Georg Thieme Verlag Stuttgart.
- Wei, Li-Mei,Wei, Li-Lan,Pan, Wen-Bin,Wu, Ming-Jung
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p. 2219 - 2223
(2007/10/03)
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- Trimethylsilylphenylacetylene in C-Alkynylation Reactions
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Direction and yields of products of the reaction between phenylethynyl anions, generated from trimethylsilylphenylacetylene under the action of potassium fluoride in DMF, and C-electrophilic reagents (aliphatic and aromatic aldehydes and ketones, aliphatic and aromatic acyl chlorides, aryl halides, and alkenyl chlorides with chlorine in the allylic position) are controlled by their structure. Secondary acetylenic alcohols prepared from aromatic aldehydes, as well as their trimethylsilyl ethers, undergo uncatalyzed Meyer-Schuster rearrengement.
- Komissarova,Aleksandrova,Stadnichuk
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p. 412 - 416
(2007/10/03)
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- [(3-dimethylamino)propyl]dimethylaluminum: A convenient reagent for methylation and ethynylation of carbonyl compounds
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At 60-80°C the title compound methylates a variety of mono- and diketones. Aromatic aldehydes undergo simple methylation by the reagent only after initial treatment with an equivalent amount of AlCl3. Upon reaction of Me2Al(CH2)3NMe2 with terminal acetylenes the aluminum complex is converted into a carbonyl-alkynylation reagent.
- Baidossi, Wael,Rosenfeld, Ayelet,Wassermann, Brigit C.,Schutte, Stefan,Schumann, Herbert,Blum, Jochanan
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p. 1127 - 1130
(2007/10/03)
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- LICKOR-Promoted 1,2-elimination in 1,1-dimethoxy-2-phenylethane and 1,1-dimethoxy-2-phenylpropane: synthesis of substituted enol ethers and alkynes
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Dimethyl acetals of phenylacetaldehyde 1a and 2-phenylpropionaldehyde 1b, upon treatment with 1.25 equiv. of LICKOR reagent, undergo 1,2-elimination (THF at -95 deg C) promoted by metallation at the benzylic site, and afford the corresponding enol ethers in the E-form.When the substrate is treated with excess of the base (2.5 equiv.), further hydrogen-metal exchange takes place at the α-vinyl site of the elimination product, and carbonyl electrophiles can be added to the carbanionic intermediate yielding allyl alcohols.Experimental procedures are given for the conversion of the α-substituted derivatives into carbonyl compounds, according to an inverse polarity approach.Moreover, allyl alcohols synthesized starting from 1a, can be transformed into prop-2-ynyl alcohols by treatment with LICKOR base.
- Deagostino, Annamaria,Mella, Mariella,Prandi, Cristina,Venturello, Paolo
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p. 2757 - 2760
(2007/10/02)
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- Synthesis of 3-Benzoyl-3,4-dihydro-2H- and 3,4-Dihydro-2,2-disubstituted benzopyrans via Alkynyl Grignard Reagents
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The versatility of the new route to a substituted chromane via a lithiated allene recently described by us is reported.The relatively more stable alkynols 2-4 were readily identified and thus provide evidence for the formation of vinyl acetylene carbinol
- Adegoke, Emmanuel A.,Emokpae, T. A.,Ephraim-Bassey, H.,Oyelola, C. A.
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p. 1705 - 1708
(2007/10/02)
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