- Alcohol Dehydrogenases and N-Heterocyclic Carbene Gold(I) Catalysts: Design of a Chemoenzymatic Cascade towards Optically Active β,β-Disubstituted Allylic Alcohols
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The combination of gold(I) and enzyme catalysis is used in a two-step approach, including Meyer–Schuster rearrangement of a series of readily available propargylic alcohols followed by stereoselective bioreduction of the corresponding allylic ketone intermediates, to provide optically pure β,β-disubstituted allylic alcohols. This cascade involves a gold N-heterocyclic carbene and an enzyme, demonstrating the compatibility of both catalyst types in aqueous medium under mild reaction conditions. The combination of [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene][bis(trifluoromethanesulfonyl)-imide]gold(I) (IPrAuNTf2) and a selective alcohol dehydrogenase (ADH-A from Rhodococcus ruber, KRED-P1-A12 or KRED-P3-G09) led to the synthesis of a series of optically active (E)-4-arylpent-3-en-2-ols in good yields (65–86 %). The approach was also extended to various 2-hetarylpent-3-yn-2-ol, hexynol, and butynol derivatives. The use of alcohol dehydrogenases of opposite selectivity led to the production of both allyl alcohol enantiomers (93->99 % ee) for a broad panel of substrates.
- González-Granda, Sergio,Lavandera, Iván,Gotor-Fernández, Vicente
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supporting information
p. 13945 - 13951
(2021/04/22)
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- Dual Palladium/Copper-Catalyzed anti-Selective Intermolecular Allenylsilylation of Terminal Alkynes: Entry to (E)-Silyl Enallenes
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A palladium-/copper-cocatalyzed three-component trans-allenylsilylation of terminal alkynes with propargyl acetates and PhMe2SiBpin is described, which is driven by the regioselective allenylation of the alkyne with propargyl acetates and then silylation. This method allows the simultaneous incorporation of an allene and silicon across the CC bond and provides a highly chemo-, regio-, and stereoselective alkyne difunctionalization route to the synthesis of valuable (E)-silyl enallenes. The utility of this method is highlighted by late-stage derivatization of bioactive compounds.
- Yang, Liang-Feng,Wang, Qiu-An,Li, Jin-Heng
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supporting information
p. 6553 - 6557
(2021/09/02)
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- Rhodium-Catalyzed and Chiral Zinc Carboxylate-Assisted Allenylation of Benzamides via Kinetic Resolution
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Enantioenriched allenes are important building blocks. While they have been accessed by other coupling methodologies, enantioenriched allenes have been rarely obtained via C-H activation. In this work, kinetic resolution of tertiary propargyl alcohols as an allenylating reagent has been realized via rhodium(III)-catalyzed C-H allenylation of benzamides. The reaction proceeded efficiently under mild conditions, and both the allenylated products and the propargyl alcohols were obtained in high enantioselectivities with an s-factor of up to 139. The resolution results from bias of the two propargylic substituents and is assisted by a chiral zinc carboxylate additive.
- Mao, Ruxia,Zhao, Yanliang,Zhu, Xiaohan,Wang, Fen,Deng, Wei-Qiao,Li, Xingwei
-
supporting information
p. 7038 - 7043
(2021/09/18)
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- Method for preparing ethynylnaphthalene derivatives by [4 + 2] cyclization reaction with water as solvent
-
The invention discloses a [4 + 2] cyclization reaction with water as a solvent to prepare a naphthalene derivative and application thereof. The synthesis method comprises the following steps: taking an alkyne compound and butyne diacid diester as a reacti
- -
-
Paragraph 0038-0059
(2021/09/11)
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- Rhodium-Catalyzed Annulation of Phenacyl Ammonium Salts with Propargylic Alcohols via a Sequential Dual C-H and a C-C Bond Activation: Modular Entry to Diverse Isochromenones
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Given their omnipresence in natural products and pharmaceuticals, isochromenone congeners are one of the most privileged scaffolds to synthetic chemists. Disclosed herein is a dual (ortho/meta) C-H and C-C activation of phenacyl ammonium salts (acylammonium as traceless directing group) toward annulation with propargylic alcohols to accomplish rapid access for novel isochromenones by means of rhodium catalysis from readily available starting materials. This operationally simple protocol features broad substrate scope and wide functional group tolerance. Importantly, the protocol circumvents the need of any stoichiometric metal oxidants and proceeds under aerobic conditions.
- Nanubolu, Jagadeesh Babu,Reddy Singam, Maneesh Kumar,Sridhar Reddy, Maddi,Suresh, Vavilapalli,Suri Babu, Undamatla
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supporting information
p. 7888 - 7893
(2021/10/25)
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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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- 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
-
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
-
supporting information
(2020/04/22)
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- Organocatalytic Formal (3 + 2) Cycloaddition toward Chiral Pyrrolo[1,2- a]indoles via Dynamic Kinetic Resolution of Allene Intermediates
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We report the chiral phosphoric acid catalyzed formal (3 + 2) cycloaddition of 3-substituted 1H-indoles and propargylic alcohols containing a functional directing group (p-NHAc or p-OH). This work represents a straightforward method to synthesize chiral pyrrolo[1,2-a]indole bearing a tetrasubstituted carbon stereocenter. The reaction proceeds smoothly with a wide array of substrate tolerance to deliver various chiral pyrrolo[1,2-a]indoles in up to 93percent yield and 98percent ee. The utility of this method is highlighted by the diverse transformations of the products into various indole derivatives.
- Bai, Jian-Fei,Zhao, Lulu,Wang, Fang,Yan, Fachao,Kano, Taichi,Maruoka, Keiji,Li, Yuehui
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supporting information
p. 5439 - 5445
(2020/07/14)
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- Fluorescent dye containing phenylacetylene naphthalene as well as preparation method and application of fluorescent dye
-
The invention relates to a fluorescent dye containing phenylacetylene naphthalene, a preparation method and an application thereof, the chemical structural formula of the fluorescent dye containing phenylacetylene naphthalene is shown in the specification
- -
-
Paragraph 0032-0034
(2020/07/21)
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- Copper-Catalyzed Radical 1,4-Difunctionalization of 1,3-Enynes with Alkyl Diacyl Peroxides and N-Fluorobenzenesulfonimide
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Many reactions involving allenyl ion species have been studied, but reactions involving allenyl radicals are less well understood, perhaps because of the inconvenience associated with the generation of short-lived allenyl radicals. We describe here a versatile method for the generation of allenyl radicals and their previously unreported applications in the intermolecular 1,4-carbocyanation and 1,4-sulfimidocyanation of 1,3-enynes. With the assistance of the trifunctional reagents, alkyl diacyl peroxides or N-fluorobenzenesulfonimide, a range of synthetically challenging multisubstituted allenes can be prepared with high regioselectivity. These multisubstituted allenes can be easily transformed into synthetically useful structures such as fluorinated vinyl cyanides, lactones, functionalized allenyl amides, 1-aminonaphthalenes, and pyridin-2(1H)-ones, and several novel transformations are reported. The results of radical scavenger and radical clock experiments are consistent with the proposed allenyl radical pathway. Density functional theory (DFT) and IR spectroscopy studies suggest the formation of an isocyanocopper(II) species in the ligand exchange step. On the basis of the results of IR, DFT, and diastereoselectivity studies, an isocyanocopper(II)/copper(I) catalytic cycle is proposed, which differs from the previously considered Cu(III) mechanism in cyanation reactions.
- Zhu, Xiaotao,Deng, Weili,Chiou, Mong-Feng,Ye, Changqing,Jian, Wujun,Zeng, Yuehua,Jiao, Yihang,Ge, Liang,Li, Yajun,Zhang, Xinhao,Bao, Hongli
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supporting information
p. 548 - 559
(2019/01/04)
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- Regiospecific formal [3 + 2] annulation of: Tert -propargyl alcohols with acyclic 1,3-diketones via the cycloisomerization of homoallenyl ketones
-
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
-
supporting information
p. 1924 - 1928
(2019/02/20)
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- Synthesis of 4-Oxoisoxazoline N-Oxides via Pd-Catalyzed Cyclization of Propargylic Alcohols with tert-Butyl Nitrite
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A cyclization of propargylic alcohols with tert-butyl nitrite at room temperature in air was achieved using Pd(OAc)2 as catalyst. The first reported 4-oxoisoxazoline N-oxides could be directly accessed from a range of multisubstituted propargylic alcohols in moderate to excellent yields under mild conditions. Density functional theory calculations indicated that the reaction proceeds through a palladium-catalyzed NO2 addition that efficiently generates a ketoxime radical, which eventually produces 4-oxoisoxazoline N-oxide.
- Feng, Kai-Wen,Ban, Yong-Liang,Yuan, Pan-Feng,Lei, Wen-Long,Liu, Qiang,Fang, Ran
-
supporting information
p. 3131 - 3135
(2019/05/10)
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- Palladium(II)/Lewis acid cocatalyzed oxidative annulation of 2-alkenylanilines and propargylic esters: An access to benzo[ b]azepines
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An attractive approach to valuable yet synthetically challenging benzo[b]azepines was established via palladium(II)/Lewis acid cocatalyzed oxidative [5 + 2] annulation of readily available 2-alkenylanilines and propargylic esters. The protocol features mild reaction conditions and good functional group tolerance, constituting an array of benzo[b]azepines in yields of 30-75%.
- Qiao, Hong,Zhang, Shengjun,Li, Kangkang,Cao, Zhengqiang,Zeng, Fanlong
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p. 10843 - 10851
(2019/09/12)
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- Neighboring Carbonyl Group Assisted Hydration of Unsymmetrical Aryl Alkynes Overriding Regular Selectivity
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A mild and highly regioselective gold-catalyzed hydration of γ-acetoxy aryl alkynes leading to anti-Markovnikov products by the assistance of a neighboring carbonyl group is presented. The reaction procedure operates under room temperature conditions with
- Mendhekar, Kishor L.,Pradhan, Tapas R.,Mallampudi, N. Arjunreddy,Mohapatra, Debendra K.
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p. 5787 - 5797
(2019/08/21)
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- Synthesis of 2-(Isoquinolin-1-yl)prop-2-en-1-ones via Silver(I)-Catalyzed One-Pot Tandem Reaction of ortho-Alkynylbenzaldoximes with Propargylic Alcohols
-
The silver(I)-catalyzed reaction of ortho-alkynylbenzaldoximes with propargylic alcohols represents a new strategy for the divergent one-pot synthesis of 2-(isoquinolin-1-yl) prop-2-en-1-ones via tandem 6-endo-cyclization, 1,3-dipolar cycloaddition, and intramolecular dehydrative opening of the 2,3-dihydroisoxazole ring. This synthetic protocol tolerates a wide variety of ortho-alkynylbenzaldoximes and propargylic alcohols and affords the corresponding products in excellent yields.
- Nikbakht, Ali,Balalaie, Saeed,Breit, Bernhard
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supporting information
p. 7645 - 7648
(2019/10/14)
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- Alkynylaluminum Synthesis Catalyzed by a Zwitterionic Neodymium(III) Heterobimetallic Compound
-
The reaction of H{PhB(OxMe2)2C5H5} (OxMe2 = 4,4-dimethyl-2-oxazoline) with Nd(AlMe4)3 (1) provides Me2Al{(OxMe2)2PhBCp}Nd(AlMe4)2
- Kanbur, Uddhav,Ellern, Arkady,Sadow, Aaron D.
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p. 4409 - 4414
(2019/01/03)
-
- SeCl2-Mediated Approach Toward Indole-Containing Polysubstituted Selenophenes
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A novel and efficient SeCl2-mediated chalcogenative cyclization strategy toward 3-selenophen-3-yl-1H-indoles from readily available and conveniently substituted propargyl indoles is described. It entails an unprecedented selenirenium-induced 1,
- Martins, Guilherme M.,Back, Davi F.,Kaufman, Teodoro S.,Silveira, Claudio C.
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p. 3252 - 3264
(2018/03/25)
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- Iron-Catalyzed Dehydrative Alkylation of Propargyl Alcohol with Alkyl Peroxides to Form Substituted 1,3-Enynes
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This paper reports a new method for the generation of substituted 1,3-enynes, whose synthesis by other methods could be a challenge. The dehydrative decarboxylative cascade coupling reaction of propargyl alcohol with alkyl peroxides is enabled by an iron catalyst and alkylating reagents. Primary, secondary, and tertiary alkyl groups can be introduced into 1,3-enynes, affording various substituted 1,3-enynes in moderate to good yields. Mechanistic studies suggest the involvement of a radical-polar crossover pathway.
- Ye, Changqing,Qian, Bo,Li, Yajun,Su, Min,Li, Daliang,Bao, Hongli
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supporting information
p. 3202 - 3205
(2018/06/11)
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- Direct Substitution of Secondary and Tertiary Alcohols to Generate Sulfones under Catalyst- and Additive-Free Conditions
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An environmentally benign protocol that affords propargylic sulfones containing highly congested carbon centers from easily accessible alcohols and sulfinic acids with water as the only byproduct is reported. The reaction proceeded via an in situ dehydrative cross-coupling process by taking advantage of the synergetic actions of multiple hydrogen bonds rather than relying on an external catalyst and/or additives to achieve high product distribution.
- Liu, Yanan,Xie, Peizhong,Sun, Zuolian,Wo, Xiangyang,Gao, Cuiqing,Fu, Weishan,Loh, Teck-Peng
-
supporting information
p. 5353 - 5356
(2018/09/13)
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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
-
supporting information
p. 15043 - 15056
(2019/01/04)
-
- Alkynylation of aldehydes mediated by zinc and allyl bromide: a practical synthesis of propargylic alcohols
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Abstract: A practical synthesis of propargylic alcohols was developed by alkynylation of aldehydes mediated by zinc and allyl bromide. Aromatic, aliphatic and vinyl aldehydes react with phenylacetylene or 1-hexyne to obtain various propargylic alcohols at room temperature in up to 98% yield. This method is characterized with inexpensive materials, wide substrate scope, and mild reaction conditions, and is also easy to scale up. In addition, this protocol is applicable to the alkynylation of α-ketone esters and epoxides to generate α-tertiary-hydroxy esters and α-alkynyl alcohols, respectively. Graphical Abstract: [Figure not available: see fulltext.].
- Zhou, Ji-Cai,Zhao, Lei,Li, Yuan,Fu, Ding-Qiang,Li, Zi-Cheng,Huang, Wen-Cai
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p. 4283 - 4294
(2017/06/20)
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- Fe(OTf)3-catalyzed tandem Meyer-Schuster rearrangement/intermolecular hydroamination of 3-aryl propargyl alcohols for the synthesis of acyclic β-Aminoketones
-
Fe(OTf)3-catalyzed synthesis of acyclic β-aminoketones from 3-aryl propargyl alcohols and nitrogen nucleophiles were investigated. Results showed that propargyl alcohols without bulky groups α to the hydroxyl group underwent the transformation smoothly. Sulphonamides exhibited the higher reactivity than amides as the nitrogen nucleophiles and the transformation of acyclic β-aminoketones were finished in shorter reaction time and higher yields. Finally, racemic fluoxetine was efficiently accessed with the present reaction as the first step. This novel synthesis of acyclic β-aminoketones probable proceeded a Fe(OTf)3-catalyzed Meyer-Schuster rearrangement of 3-aryl propargyl alcohols, followed by a intermolecular hydroamination between nitrogen nucleophiles and α, β-unsaturated ketones.
- Tao, Ruiheng,Yin, Yan,Duan, Yongbin,Sun, Yuxing,Sun, Yue,Cheng, Fengkai,Pan, Jinpeng,Lu, Cheng,Wang, Yuan
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p. 1762 - 1768
(2017/03/08)
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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
-
supporting information
p. 3381 - 3385
(2017/06/29)
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- Palladium(II)/N-Heterocyclic Carbene-Catalyzed Regioselective Heteroannulation of Tertiary Propargyl Alcohols and o-Haloanilines to form 2-Alkenylindoles
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Monometallic and bimetallic palladium(II)/N-heterocyclic carbene complexes appended with naphthalimide or bisnaphthalimide moieties were designed, synthesized, and characterized. Employment of these catalysts brings about the step-economic and regioselective heteroannulation of tertiary propargyl alcohols with o-haloanilines resulting in biologically and pharmaceutically relevant 2-alkenylindoles. Basis for the regioselective heteroannulation is unraveled by coordination of the propargylic hydroxy moiety to palladium during insertion. Embracing this methodology, a single regioisomer of unsymmetrical 2,3-disubstituted indoles could be achieved through late-stage modification. The role of the naphthalimide or bisnaphthalimide appended to the NHC on the catalytic efficiency has been studied. (Figure presented.).
- Panyam, Pradeep Kumar Reddy,Gandhi, Thirumanavelan
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supporting information
p. 1144 - 1151
(2017/04/13)
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- Highly Efficient Synthesis of Multi-Substituted Allenes from Propargyl Acetates and Organoaluminum Reagents Mediated by Palladium
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A simple and mild catalytic S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents is reported. The S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents mediated by Pd(PhP 3) 2 Cl 2 (1 mol%)/PPh 3 (2 mol%)/K 2 CO 3 in tetrahydrofuran at 60 °C for 3-4 hours afforded the corresponding multi-substituted allenes in good yields (up to 94%) with high selectivities (up to 99%). The process was simple and easily performed, which offers an efficient method to synthesize the multi-substituted allene derivatives.
- Zhang, Zhen,Shao, Xuebei,Zhang, Gang,Li, Qinghan,Li, Xinying
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p. 3643 - 3653
(2017/08/16)
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- Asymmetric Intermolecular Heck Reaction of Propargylic Acetates and Cycloalkenes to Access Fused Cyclobutenes
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An asymmetric Heck annulation of propargylic acetates with several types of cyclic olefins affords highly strained cyclobutenes in high enantioselectivity.
- Jiao, Zhiwei,Shi, Qi,Zhou, Jianrong Steve
-
supporting information
p. 14567 - 14571
(2017/10/23)
-
- Palladium-Catalyzed Nitration of Meyer-Schuster Intermediates with tBuONO as Nitrogen Source at Ambient Temperature
-
A novel domino palladium-catalyzed nitration of Meyer-Schuster intermediates which were generated in situ from propargylic alcohols was developed, by the use of t-BuONO, leading to α-nitro enones in good to excellent yields at room temperature with a broa
- Lin, Yuanguang,Kong, Weiguang,Song, Qiuling
-
supporting information
p. 3702 - 3705
(2016/08/16)
-
- Addition of terminal alkynes to α-ketone esters to synthesize α-tertiary-hydroxy esters promoted by zinc and an alkyl halide
-
A convenient method to synthesize various α-tertiary-hydroxy esters at room temperature has been developed. This method uses the readily available and inexpensive Zn powder in combination with an alkyl halide to promote the addition of alkynes to α-ketone
- Zhang, Wen,Cao, Yuan,Chen, Wei,Zhao, Gang,Pu, Lin
-
supporting information
p. 6430 - 6432
(2015/11/16)
-
- Gold-Catalyzed Rearrangement of Alkynyl Donor-Acceptor Cyclopropanes to Construct Highly Functionalized Alkylidenecyclopentenes
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A gold-catalyzed 1,7-addition-cyclization-elimination cascade sequence performed on a range of alkynyl-substituted donor-acceptor-type cyclopropanes provides facile entry to highly functionalized exo-alkylidenecyclopentenes under very mild conditions. Iso
- Chen, Huiyu,Zhang, Jing,Wang, David Zhigang
-
supporting information
p. 2098 - 2101
(2015/05/13)
-
- Alkynylation of aldehydes and ketones using the Bu4NOH/H 2O/DMSO catalytic composition: A wide-scope methodology
-
The Favorsky reaction of a wide range of aldehydes and ketones with alkynes has been implemented under mild conditions (5-20 C). Using a Bu 4NOH/H2O/DMSO catalytic system, propargylic alcohols are formed cleanly in 39-93% (mostly 72-93%) yields and with ca. 100% selectivity. The method is suitable for aliphatic, aromatic, and heteroaromatic aldehydes and ketones, and for aliphatic, aromatic, and functionalized acetylenes. Thus, this represents the most general and efficient protocol to achieve the Favorsky reaction. Copyright
- Schmidt, Elena Yu.,Cherimichkina, Natalia A.,Bidusenko, Ivan A.,Protzuk, Nadezhda I.,Trofimov, Boris A.
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p. 4663 - 4670
(2014/08/05)
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- Fluorinated microporous organic polymers: Design and applications in CO2adsorption and conversion
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Fluorinated microporous organic polymers (F-MOPs) were designed, showing twice higher CO2adsorption capacity than corresponding non-fluorous MOPs. The incorporation of phenanthroline moieties into F-MOPs afforded them the ability to coordinate with Ag(I), and the resultant F-MOP-Ag(I) displayed high efficiency for the reaction of CO2with propargyl alcohols to form a-alkylidene cyclic carbonates at 25°C.
- Yang, Zhen-Zhen,Zhao, Yanfei,Zhang, Hongye,Yu, Bo,Ma, Zhishuang,Ji, Guipeng,Liu, Zhimin
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supporting information
p. 13910 - 13913
(2015/02/19)
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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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- 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
-
supporting information; experimental part
p. 2844 - 2850
(2012/05/05)
-
- Efficient catalytic transition-metal-free conditions for nucleophilic addition of arylacetylenes to aromatic ketones
-
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
-
supporting information; experimental part
p. 2160 - 2163
(2012/05/05)
-
- Regioselectivity switch: Gold(I)-catalyzed oxidative rearrangement of propargyl alcohols to 1,3-diketones
-
The gold(I)-catalyzed oxidative rearrangement of propargyl alcohols provides an efficient and selective route to 1,3-diketones under mild conditions. Pyridine-N-oxides were used as external oxidants with, different from related substrates, no alkylidenecycloalkanones or oxetan-3-ones formed as side-products.
- Hashmi, A. Stephen K.,Wang, Tao,Shi, Shuai,Rudolph, Matthias
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p. 7761 - 7767
(2012/11/07)
-
- 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
-
supporting information; experimental part
p. 331 - 337
(2011/02/17)
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- Base-catalyzed stereoselective vinylation of ketones with arylacetylenes: A new C(sp3)-C(sp2) bond-forming reaction
-
Alkylaryl- and alkylheteroarylketones, including those with condensed aromatic moieties, are readily vinylated with arylacetylenes (KOH/DMSO, 100°C, 1 h) to give regio- and stereoselectively the (E)-β-γ- ethylenic ketones ((E)-3-buten-1-ones) in 61-84% yi
- Trofimov, Boris A.,Schmidt, Elena Yu,Ushakov, IgoR'A,Zorina, Nadezhda V.,Skital'Tseva, Elena V.,Protsuk, Nadezhda I.,Mikhaleva, AL'Bina I.
-
body text
p. 8516 - 8521
(2010/09/05)
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- Ytterbium(III) triflate catalyzed tandem friedel-crafts alkylation/hydroarylation of propargylic alcohols with phenols as an expedient route to indenols
-
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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- 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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- Highly enantioselective catalytic alkynylation of ketones - A convenient approach to optically active propargylic alcohols
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The development of highly enantioselective catalysts involving Cu(OTf) 2 and chiral camphorsulfonamides for the alkynylation of ketone is described. The influences of Lewis acids, reaction conditions and chiral ligands on the outcome of the rea
- Lu, Gui,Li, Xingshu,Li, Yue-Ming,Kwong, Fuk Yee,Chan, Albert S. C.
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p. 1926 - 1933
(2007/10/03)
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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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- Ultrasound-assisted synthesis of functionalized arylacetylenes
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A convenient and inexpensive ultrasound-assisted preparation of functionalized arylacetylenes using metallic lithium is reported.
- Stefani, Hélio A.,Cella, Rodrigo,D?rr, Felipe A.,De Pereira, Claudio M.P.,Gomes, Fábio P.,Zeni, Gilson
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p. 2001 - 2003
(2007/10/03)
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- Me2Zn-mediated addition of acetylenes to aldehydes and ketones
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Contrary to expectations, commercially available 2 M Me2Zn in toluene is able to promote the addition of phenylacetylene to aldehydes and ketones. This reactivity is determined by a new, unprecedented mechanism, which involves activation of the zinc reagent via coordination with carbonyl substrates that behave "ligand like". Broad scope, high tolerance to functional groups, and a simple procedure make this new method highly interesting for the synthetic chemist.
- Cozzi, Pier Giorgio,Rudolph, Jens,Bolm, Carsten,Norrby, Per-Ola,Tomasini, Claudia
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p. 5733 - 5736
(2007/10/03)
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- Organocatalytic alkynylation of aldehydes and ketones under phase-transfer catalytic conditions
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We developed alkynylations of various aldehydes and ketones under practical phase-transfer conditions at room temperature. The straightforward methodology combines one-pot synthesis and simple workup with good to excellent yields for propargylic alcohols derived from aliphatic aldehydes and ketones. Even aromatic aldehydes and ketones, could be transformed to the corresponding propargylic alcohols in somewhat lower yields. The yield depending on the amount of PT catalyst and NaOH concentration was also determined. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).
- Weil, Torsten,Schreiner, Peter R.
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p. 2213 - 2217
(2007/10/03)
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- Catalytic alkynylation of ketones and aldehydes using quaternary ammonium hydroxide base
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Catalytic alkynylation of diverse ketones and aldehydes using nonmetallic benzyltrimethylammonium hydroxide or a basic resin of the hydroxide type in DMSO is described. Aliphatic or alicyclic carbonyl partners gave satisfactory results, whereas aromatic o
- Ishikawa, Teruhiko,Mizuta, Tomohiro,Hagiwara, Kumiko,Aikawa, Toshiaki,Kudo, Takayuki,Saito, Seiki
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p. 3702 - 3705
(2007/10/03)
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- Indium-mediated carbonyl alkynylation
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Indium mediates a Barbier-type reaction between alkynyl halides and aldehydes or ketones to give secondary or tertiary propargyl alcohols. Secondary alcohols can be oxidised in situ according an Oppenauer process.
- Augé, Jacques,Lubin-Germain, Nadège,Seghrouchni, Latifa
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p. 5255 - 5256
(2007/10/03)
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- Tertiary acetylenic alcohols and diols on the basis of phenylacetylene and 2-methyl-3-butyn-2-ol
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A procedure has been proposed for the synthesis of tertiary acetylenic alcohols and diols by treatment of phenylacetylene or 2-methyl-3-butyn-2-ol with butyllithium and subsequent reaction of lithium phenylacetylide or lithium 4-lithio-2-methyl-3-butyn-2-
- Potkin,Dikusar,Kozlov
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p. 1260 - 1265
(2007/10/03)
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- Solvent-free addition of ethynylbenzene to ketones
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The addition of ethynylbenzene to ketones proceeded efficiently in the absence of a solvent to give tertiary alkynols in good yields.
- Miyamoto,Yasaka,Tanaka
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p. 185 - 186
(2007/10/03)
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- Generation and reactions of alkynylsamariums
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Three methods have been developed for generating alkynylsamariums: (1) reduction of iodoalkynes with SmI2 in the presence of HMPA, (2) deprotonation at the terminal position of 1-alkynes either by tetrahydrofurylsamarium generated by PhI and Sm
- Kunishima, Munetaka,Nakata, Daisuke,Tanaka, Shinobu,Hioki, Kazuhito,Tani, Shohei
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p. 9927 - 9935
(2007/10/03)
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