- Nickel-catalyzed carbometalation reactions of [2-(1-propynyl)phenyl] methanol with 1-alkenylmagnesium reagents
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Treatment of [2-(1-propynyl)phenyl]methanol with 1-alkenyl Grignard reagents under nickel catalysis results in carbomagnesiation across the alkynyl part. The 1-alkenylation reaction proceeds in a syn fashion to yield the corresponding 1,3-butadienyl-subst
- Murakami, Kei,Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
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- Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides
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A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step.
- Li, Ming-Ming,Cheng, Lei,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 2948 - 2951
(2020/12/15)
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- Selective 1,2-Aminoisothiocyanation of 1,3-Dienes Under Visible-Light Photoredox Catalysis
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Selective three-component 1,2-diamination of 1,3-dienes with concurrent introduction of two orthogonally protected amino groups remains unknown despite its significant synthetic potential. We report herein that reaction of conjugated dienes with N-aminopy
- Guo, Weisi,Wang, Qian,Zhu, Jieping
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supporting information
p. 4085 - 4089
(2020/12/25)
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- Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling
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The construction of carbon-heteroatom bonds is one of the most active areas of research in organic chemistry because the function of organic molecules is often derived from the presence of heteroatoms. Although considerable advances have recently been achieved in radical-involved catalytic asymmetric C-N bond formation, there has been little progress in the corresponding C-O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling of readily available oxime esters and 1,3-dienes to generate diversely substituted allylic esters with high regio- and enantioselectivity (>75 examples; up to 95% ee). The reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) and features the use of a single, earth-abundant copper-based chiral catalyst as both the photoredox catalyst for radical generation and the source of asymmetric induction in C-O coupling. Combined experimental and density functional theory (DFT) computational studies suggest the formation of π-allylcopper complexes from redox-active oxime esters as bifunctional reagents and 1,3-dienes through a radical-polar crossover process.
- Chen, Jia-Rong,Chen, Jun,Guan, Wei,Huan, Xiao-Die,Li, Guo-Qing,Liang, Yu-Jie,Qian, Hao,Wang, Peng-Zi,Xiao, Wen-Jing,Zhang, Bin
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supporting information
p. 13382 - 13392
(2021/09/03)
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- Ni-Catalyzed Regioselective Hydroarylation of 1-Aryl-1,3-Butadienes with Aryl Halides
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An efficient nickel-catalyzed regioselective hydroarylation of 1,3-dienes with aryl halides and a silane has been developed, affording a range of allylic arenes in good to excellent yields under mild conditions. This method exhibits broad substrate scope,
- Wang, Chengdong,Guo, Yingjie,Wang, Xiaoming,Wang, Zheng,Ding, Kuiling
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supporting information
p. 15903 - 15907
(2021/10/07)
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- Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost of Benzotriazoles with 1,3-Dienes
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The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, bec
- Li, Yin-Lin,Wu, Hai-Hong,Zhang, Junliang,Zhang, Pei-Chao
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supporting information
p. 13010 - 13015
(2021/09/07)
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- Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and beyond
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A photoinduced palladium-catalyzed 1,2-carbofunctionalization of conjugated dienes has been developed. This mild modular approach, which does not require employment of exogeneous photosensitizers and external oxidants, allows for efficient and highly regio- and stereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl iodides, and amines. Employment of O- and C-nucleophiles toward oxyalkylation and dialkylation products was also demonstrated. A putative π-allyl palladium radical-polar crossover path is proposed as a key event in this three-component coupling process. The utility of this protocol is highlighted by its application for derivatization of several amine-containing drugs.
- Gevorgyan, Vladimir,Kurandina, Daria,Shing Cheung, Kelvin Pak,Yata, Tetsuji
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supporting information
p. 9932 - 9937
(2020/06/27)
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- Stereoselective and Atom-Economic Alkenyl C-H Allylation/Alkenylation in Aqueous Media by Iridium Catalysis
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A practical and atom-economic protocol for the stereoselective preparation of various 1,4-and 1,3-diene skeletons through iridium-catalyzed directed olefinic C-H allylation and alkenylation of NH-Ts acrylamides in water was developed. This reaction tolerated a wide scope of substrates under simple reaction conditions and enabled successful gram-scale preparation. Furthermore, an asymmetric variant of this reaction giving enantioenriched 1,4-dienes was achieved employing a chiral diene-iridium complex as the catalyst.
- Ding, Liyuan,Huang, Yinhua,Lu, Xiunan,Shen, Wenzhou,Xu, Liangyao,Yu, Feifei,Zhang, Jian,Zhong, Guofu,Zhong, Liangjun
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p. 7225 - 7237
(2020/07/07)
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- Transition-Metal-Free Allylic Borylation of 1,3-Dienes
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This work explains the reactivity of diboron reagents with 1,3-dienes in a transition-metal-free context. The sole addition of Na2CO3 (30 mol %) to bis(pinacolato)diboron in MeOH allows the 1,4-hydroboration of cyclic and noncyclic 1,3-dienes. The electronic influence on the substrate guarantees the conjugated 1,4-hydroboration versus 1,2-diboration. DFT calculations show that the distribution of charge in the allylic anion intermediate governs the selectivity toward 1,4-hydroboration, while the favored trans configuration in diene reagents determines the preference for the E allyl boronate products.
- Maza, Ricardo J.,Davenport, Elliot,Miralles, Núria,Carbó, Jorge J.,Fernández, Elena
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supporting information
p. 2251 - 2255
(2019/04/10)
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- Iridium-catalyzed alkenyl C-H allylation using conjugated dienes
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An iridium-catalyzed C-H allylation of acrylamides with conjugated dienes was developed, using NH-Ts amide as the directing group. The ligand- and additive-free protocol provided a convenient and atom economic synthesis of branched 1,4-diene skeletons, enabling the tolerance of a wide scope of functionalities such as OMe, F, Cl, Br and CF3. The utility of this protocol is also demonstrated by a preparative scale, as well as C-H functionalization of artemisic amide. Furthermore, NH-Ts amide was efficiently removed by methylation and hydrolysis procedures to provide 1,4-dienoic acid.
- Xu, Liangyao,Meng, Keke,Zhang, Jian,Sun, Yaling,Lu, Xiunan,Li, Tingyan,Jiang, Yan,Zhong, Guofu
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supporting information
p. 9757 - 9760
(2019/08/20)
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- Palladium-Catalyzed Chemoselective Protodecarboxylation of Polyenoic Acids
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Conditions for the first palladium-catalyzed chemoselective protodecarboxylation of polyenoic acids to give the desired polyenes in good yields are presented. The reactions proceed under mild conditions using either a Pd(0) or Pd(II) catalyst and tolerate a variety of aryl and aliphatic substitutions. Unique aspects of the reaction include the requirement of phosphines, water, and a polyene adjacent to the carboxylic acid.
- Al-Huniti, Mohammed H.,Perez, Mark A.,Garr, Matthew K.,Croatt, Mitchell P.
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supporting information
p. 7375 - 7379
(2019/01/03)
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- Transition-metal-free synthesis of vicinal triborated compounds and selective functionalisation of the internal C-B bond
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1,2,3-Triborated compounds can be prepared by simple nucleophilic borylation of 1,3-dienes, without the assistance of metal catalysts. Selective functionalisation of the internal C-B bond of the 1,2,3-triborated compounds, through cross-coupling with aryl
- Davenport, Elliot,Fernandez, Elena
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supporting information
p. 10104 - 10107
(2018/09/18)
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- Ni-Catalyzed Site-Selective Dicarboxylation of 1,3-Dienes with CO2
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A site-selective catalytic incorporation of multiple CO2 molecules into 1,3-dienes en route to adipic acids is described. This protocol is characterized by its mild conditions, excellent chemo- and regioselectivity and ease of execution under CO2 (1 atm), including the use of bulk butadiene and/or isoprene feedstocks.
- Tortajada, Andreu,Ninokata, Ryo,Martin, Ruben
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supporting information
p. 2050 - 2053
(2018/02/19)
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- Cobalt-Catalyzed Coupling of Benzoic Acid C?H Bonds with Alkynes, Styrenes, and 1,3-Dienes
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A method for cobalt-catalyzed, carboxylate-directed functionalization of arene C?H bonds is reported. Alkynes, styrenes, and 1,3-dienes can be coupled with benzoic acids to provide cyclic products in good yields. The reactions proceed in the presence of a
- Nguyen, Tung Thanh,Grigorjeva, Liene,Daugulis, Olafs
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supporting information
p. 1688 - 1691
(2018/01/15)
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- Styrylmalonates as an Alternative to Donor-Acceptor Cyclopropanes in the Reactions with Aldehydes: A Route to 5,6-Dihydropyran-2-ones
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A new strategy for modifying the reactivity of donor-acceptor cyclopropanes (DAC) has been suggested. It involves the use of isomeric styrylmalonates as alternative sources of reactive intermediates. The efficiency of the approach has been demonstrated in reactions with aromatic aldehydes. As a result, a new process for construction of the 5,6-dihydropyran-2-one skeleton has been developed. It efficiently occurs with high diastereoselectivity in the presence of BF3·Et2O; the products can be easily isolated by crystallization. The subsequent use of the resulting dihydropyranones in syntheses providing convenient access to various classes of compounds with broad molecular diversity has been demonstrated.
- Borisov, Denis D.,Novikov, Roman A.,Eltysheva, Anna S.,Tkachev, Yaroslav V.,Tomilov, Yury V.
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supporting information
p. 3731 - 3734
(2017/07/26)
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- Organoselenium-Catalyzed Regioselective C?H Pyridination of 1,3-Dienes and Alkenes
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An efficient approach for organoselenium-catalyzed regioselective C?H pyridination of 1,3-dienes to form pyridinium salts has been developed. This method was also successfully applied to direct C?H pyridination of alkenes. Fluoropyridinium reagents, or initially loaded pyridine derivatives, acted as pyridine sources in the pyridination reactions. The obtained pyridinium salts could be further converted under different conditions. This work is the first example of catalytic C-2 direct C?H functionalization of 1,3-dienes and the first case of organoselenium-catalyzed C?H pyridination.
- Liao, Lihao,Guo, Ruizhi,Zhao, Xiaodan
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p. 3201 - 3205
(2017/03/17)
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- Cobalt-Catalyzed Carbonylative Cross-Coupling of Alkyl Tosylates and Dienes: Stereospecific Synthesis of Dienones at Low Pressure
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Despite advances in organometallic cross-coupling of alkyl electrophiles, there are few stereoselective reactions of chiral, nonracemic substrates. Herein we report a stereospecific carbonylative coupling of alkyl tosylates and dienes producing enantioenriched dienones. This catalytic process proceeds under low pressure and mild conditions using a simple cobalt catalyst and extends to diverse tosylate and diene coupling partners. The transformation constitutes a unique, convergent approach to the asymmetric synthesis of valuable carbonyl compounds from easily accessed starting materials.
- Sargent, Brendon T.,Alexanian, Erik J.
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supporting information
p. 12438 - 12440
(2017/09/25)
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- A biosynthetically inspired route to substituted furans using the Appel reaction: Total synthesis of the furan fatty acid F5
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Appel reaction conditions have been harnessed to affect a mild biosynthetically inspired dehydration of endoperoxides to deliver multi-substituted electron rich furans. Unlike traditional dehydrative procedures, this method is metal and acid free, and can be achieved under redox neutral conditions. It is general for a range of aryl and alkyl substituted endoperoxides, and is functional group tolerant. Furthermore, this procedure has been used to deliver an effective total synthesis of the furan fatty acid (FFA) F5.
- Lee, Robert J.,Lindley, Martin R.,Pritchard, Gareth J.,Kimber, Marc C.
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supporting information
p. 6327 - 6330
(2017/07/11)
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- Catalyst Controlled Regiodivergent Arylboration of Dienes
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A method for the regiodivergent arylboration of dienes is presented. These reactions allow for the formation of a diverse range of synthetically versatile products from simple precursors. Through mechanistic studies, these reactions likely operate by init
- Sardini, Stephen R.,Brown, M. Kevin
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supporting information
p. 9823 - 9826
(2017/08/02)
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- LSD1 INHIBITORS AND USES THEREOF
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Provided are novel compounds of Formula (I) and pharmaceutically acceptable salts thereof, which are useful for treating a variety of diseases, disorders or conditions, associated with LSDl. Also provided are pharmaceutical compositions comprising the novel compounds of Formula (I), pharmaceutically acceptable salts thereof, and methods for their use in treating one or more diseases, disorders or conditions, associated with LSDl.
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Paragraph 00590-00591
(2016/11/17)
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- A direct synthesis of functionalized styrenes and terminal 1,3-dienes via aqueous Wittig chemistry with formalin
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A direct synthesis of functionalized styrenes including synthetically valuable styryl halides and terminal 1,3-dienes is reported directly from benzylic and allylic alcohols and aqueous formalin involving microwave assisted phosphonium salt formation and Wittig olefination under mildly basic conditions.
- Das, Priyabrata,McLeod, David,McNulty, James
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experimental part
p. 199 - 201
(2011/02/26)
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- Regioselective rhodium-catalyzed hydroformylation of 1,3-dienes to highly enantioenriched β,γ-unsaturated aldehyes with diazaphospholane ligands
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Regioselective and enantioselective rhodium-catalyzed hydroformylation of 1,3-dienes with chiral bisdiazaphospholane ligands yields β,γ- unsaturated aldehydes that retain a C=C functionality for further conversion. The reaction conditions are mild, featuring low catalyst loadings (0.5 mol %), pressures readily obtained in glass bottles, and convenient reaction times (1.5-12 h). Optimized reaction conditions produce high enantioselectivity (>90% ee), regioselectivity (88-99%), and conversion to β,γ- unsaturated aldehydes (99%) for ten 1,3-dienes encompassing a variety of substitution patterns.
- Watkins, Avery L.,Landis, Clark R.
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supporting information; experimental part
p. 164 - 167
(2011/04/12)
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- Facile synthesis of multisubstituted buta-1,3-dienes via Suzuki-Miyaura and Kumada cross-coupling strategy of 2,4-diiodo-buta-1-enes with arylboronic acids and Grignard reagents
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One-pot Suzuki-Miyaura-type and Kumada-type cross-coupling reactions of 2,4-diiodo-buta-l-enes with arylboronic acids and alkyl/aryl magnesium bromides were carried out in the presence of accessibly simple catalysts under mild conditions. As a result, some 1,1,2-trisubstituted buta-1,3-dienes were obtained including the Tamoxifen-type, which have potential adjuvant therapy in women who have suffered from breast cancer and cyclooxygenase-2-type (COX-2-type) inhibitors, some of which have been proved to elicit efficient anti-inflammatory analgesic activities and less adverse gastrointestinal side effects and to be very useful in the prophylactic treatment of a wide variety of cancers and neurodegenerative disorders. The Royal Society of Chemistry 2005.
- Shao, Li-Xiong,Shi, Min
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p. 1828 - 1831
(2007/10/03)
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- THE EFFECT OF THE STEREOCHEMICAL STRUCTURE OF 1,3-ALKADIENES ON THE DIRECTION OF CATALYTIC ADDITION OF POLYHALOGEN DERIVATIVES
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In the reaction of 1,3-alkadienes with methyl trichloroacetate and trichloroacetonitrile in the presence of copper(I) salts, in contrast to the analogous radical reactions, the presence of sterically screening substituents at position 1 of the diene syste
- Zubritskii, L. M.,Startsev, V. V.,Petrov, A. A.
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p. 186 - 191
(2007/10/02)
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- Stereoselective Synthesis of Terminal 1,3-Butadienes by the Condensation Reaction of Aldehydes and Ketones with the γ-Trimethylsilyl-Substituted Allylboranes
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Allylboranes 7-12, readily prepared from allenylsilanes 1-6 by hydroboration with 9-borabicyclononane, smoothly condense with aldehydes and ketones to afford, after basic or acidic workup to promote the Peterson olefination reaction, a variety of t
- Wang, Kung K.,Liu, Chin,Gu, Yu Gui,Burnett, Friedrich N.,Sattsangi, Prem D.
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p. 1914 - 1922
(2007/10/02)
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- NiCl2(dppe)-Catalyzed Geminal Dialkylation of Dithioacetals and Trimethylation of Ortho Thioesters
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NiCl2(dppe)-catalyzed cross-coupling of cinnamaldehyde dithioacetals gave the corresponding geminal dimethylation products in excellent yields.Allylic ortho thioesters afforded regioselectively the corresponding trimethylation products.The reaction may occur via an 18-electron ?-allyl intermediate, which undergoes facile reductive elimination to afford the geminal dimethylation product.Benzylic dithioacetals having an ortho amino group gave 2-isopropylanilines exclusively.The reaction of benzylic dithioacetals with EtMgBr under the same conditions yielded geminal diethylation products.
- Tzeng, Yih-Ling,Yang, Ping-Fan,Mei, Nai-Wen,Yuan, Tien-Min,Yu, Chun-Chi,Luh, Tien-Yau
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p. 5289 - 5293
(2007/10/02)
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- Nickel-Catalyzed Geminal Dimethylation of Allylic Dithioacetals
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A geminal dimethyl group is introduced regioselectively in excellent yield from the reactions of allylic dithioacetals and methylmagnesium iodide in the presence of 3 mol percent of NiCl2(dppe) in refluxing ether-benzene.
- Yang, Ping-Fan,Ni, Zhi-Jie,Luh, Tien-Yau
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p. 2261 - 2262
(2007/10/02)
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- Phenylthioallyl and Phenylthiovinyl Phosphine Oxides: Synthesis of 1-Phenylthiobutadienes and a Three-component Synthesis of Ketones
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The functionalisation of some substituted allyl and vinyl diphenylphosphine oxides is explored and routes to substituted γ-phenylthioallyl and γ-phenylthiovinyl phosphine oxides are described.These reagents are used in the synthesis of the title compounds.
- Grayson, J. Ian,Warren, Stuart,Zaslona, Alex T.
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p. 967 - 976
(2007/10/02)
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- Stereoselective Synthesis of (Z)- and (E)-1,3-Alkadienes from Aldehydes Using Organotitanium and Lithium Reagents
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titanium reagent generated easily from allyldiphenylphosphine condenses with aldehydes to give (Z)-1,3-alkadienes in a highly regio- and stereoselective manner.In contrast, lithiated allyldiphenylphosphine oxide condenses with aldehydes to give (E)-1,3-alkadienes directly and stereoselectively in good yield.Similarly, lithiated (1-buten-3-yl)diphenylphosphine oxide condenses with aldehydes to give (E)-3-methyl-1,3-alkadienes.
- Ikeda, Yoshihiko,Ukai, Junzo,Ikeda, Nobuo,Yamamoto, Hisashi
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p. 723 - 730
(2007/10/02)
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- 2-Allylisourea as a Starting Material for Palladium-Catalyzed Wittig-Type Allylidenation of Aldehydes
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2-Allylic-substituted isoureas underwent Wittig-type allylidenation of aldehydes in the presence of triphenylphosphine and 2 molpercent of to give the corresponding conjugated olefins in tolerable to good yields.
- Inoue, Yoshio,Toyofuku, Masanori,Hashimoto, Harukichi
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p. 1279 - 1280
(2007/10/02)
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- ETUDE DE L'ALKYLATION D'ORGANOLITHIENS ALLYLIQUES MONOCHLORES: SYNTHESE EN UNE ETAPE DE CHLORURES ALLYLIQUES SECONDAIRES OU TERTIAIRES ET/OU DE CHLORURES VINYLIQUES DE CONFIGURATION Z
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Chloroallyllithium and gem-chloro(methyl)allyllithium readily react with various alkylating reagents to produce, in a "one-pot" reaction, secundary or tertiary allylic chlorides and/or vinylic chlorides of Z configuration.
- Mauze, B.,Ongoka, P.,Miginiac, L.
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- Palladium-Catalyzed Syntheses of Aryl Polyenes
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The palladium-catalyzed arylation reaction has been employed to prepare a variety of mono- and diaryl 1,3-dienes and 1,3,5-trienes.The yields were good when electron withdrawing substituents were present in the aryl groups but only poor to fair when electron-donating groups were involved.Monoaryl dienes and trienes reacted well with all types of aryl halides to give mixed diaryl derivatives. 2-Bromostyrene reacts with phenylhexatriene to form 1,8-diphenyloctatetraene and with hexatriene to form 1,10-diphenyldecapentaene, but both only in about 15percent yield.
- Mitsudo, Taki-aki,Fischetti, William,Heck, Richard F.
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p. 1640 - 1646
(2007/10/02)
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- N-METHYLDITHIOPHTALIMIDE AS A HIGHLY REGIOSELECTIVE HETERO DIENOPHILE IN DIELS-ALDER REACTION
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N-Methyldithiophtalimide serves as a very reactive dienophile and reacts with 1,3-dienes at room temperature to give Diels-Alder products in very high regioselectivity.Stereoselectivity and retro-Diels-Alder of products are referred to.
- Tamaru, Yoshinao,Satomi, Hiroshi,Kitao, Osamu,Yoshida, Zen-ichi
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p. 2561 - 2564
(2007/10/02)
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- COMPLEXES OF TRANSITION METALS IN THE CHEMISTRY OF CONJUGATED SYSTEMS. III. REACTION OF DIENE HYDROCARBONS WITH ORGANOMAGNESIUM COMPOUNDS IN THE PRESENCE OF SALTS AND COMPLEXES OF TRANSITION METALS
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The effect of the structure of the reagents and the nature of the catalyst on the direction and selectivity in the reaction of 1,3-dienes and their derivatives with aromatic Grignard reagents was investigated.It was shown that in the presence of salts and complexes of iron(III) 1,3-alkadienes R1CH=C(R2)C(R3)=CH2 react with arylmagnesium halides to form trans-(E)-1-aryl-1,3-alkadienes, whereas the sterically hindered (R2, R3=CH3) cyclic 1,3-alkadienes and also 1,2-alkadienes give mainly adducts (1:1).Catalysis by the phosphine complexes of nickel(II) leads to the formation of telomeric (2:1) (E)-1-aryl-2,7- and (E,E)-1-aryl-2,6-alkadienes.The results demonstrate the determining role of the stereochemical conditions for the coordination of the diene in the course of the reaction and also the significant contribution from the processes of one-electron reduction of the catalyst.
- Zubritskii, L. M.,Romashchenkova, N. D.,Petrov, A. A.
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p. 2157 - 2167
(2007/10/02)
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- DIRECT, STEREOSELECTIVE SYNTHESIS OF EITHER E- OR Z-1,3-DIENES
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New synthetic methods for the preparation of Z- or E-1,3-dienes are described.
- Ukai, Junzo,Ikeda, Yoshihiko,Ikeda, Nobou,Yamamoto, Hisashi
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p. 4029 - 4032
(2007/10/02)
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