- Visible-Light-Induced, Palladium-Catalyzed 1,4-Difunctionalization of 1,3-Dienes with Bromodifluoroacetamides
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A highly modular 1,4-difunctionalization of 1,3-dienes with bromodifluoroacetamides and sulfinates/amines through a photoinduced palladium-catalyzed radical relay process is described herein. This developed protocol offers a facile and general route to ac
- Chen, Kai,Chen, Yi-Xuan,Guan, Jian-Ping,Liu, Zhi-Lin,Xiang, Hao-Yue,Xiao, Jun-An,Xie, Zhen-Zhen,Yang, Hua,Ye, Zhi-Peng,Zheng, Yu
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supporting information
p. 924 - 928
(2022/02/05)
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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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- Copolymerization of 1,3-butadiene with phenyl/phenethyl substituted 1,3-butadienes: a direct strategy to access pendant phenyl functionalized polydienes
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Copolymerization of 1,3-butadiene with various types of phenyl substituted 1,3-butadiene derivatives, including (E)-1-phenyl-1,3-butadiene (PBD), 1-phenethyl-1,3-butadiene (PEBD), 1-(4-methoxylphenyl)-1,3-butadiene (p-MEPBD), 1-(2-methoxylphenyl)-1,3-buta
- Li, Dexin,Lin, Juan,Liu, Heng,Wang, Feng,Zhang, Chunyu,Zhang, Xuequan
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p. 23184 - 23191
(2021/07/13)
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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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- Nickel-Catalyzed Carboxylation of Conjugated Dienes with Carbon Dioxide and DIBAL-H for the Synthesis of β,γ-Unsaturated Carboxylic Acids
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Conjugated dienes underwent Ni-catalyst-promoted 1,2-hydrocarboxylation in a 1:1 ratio with carbon dioxide under atmospheric pressure in the presence of diisobutylaluminum hydride (DIBAL-H) to give the corresponding β,γ-unsaturated carboxylic acids, without dimerization or oligomerization of the conjugated diene.
- Luo, Ying,Chan, Bun,Fukuda, Tsutomu,Onodera, Gen,Kimura, Masanari
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supporting information
p. 1551 - 1554
(2021/01/21)
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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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- Cu-Catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-dienes with CO2
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A practical copper-catalyzed highly regioselective 1,2-hydrocarboxylation of terminal 1,3-diene with carbon dioxide has been developed. Under mild reaction conditions, this chemistry afforded 2-benzyl-β,γ-unsaturated acid derivatives as products, which are a kind of important unit for bio-active molecules and versatile precursors for organic synthesis, with good functional group tolerance. The key intermediate in this transformation is illustrated by control experiments.
- Zhang, Penglin,Zhou, Zhanglang,Zhang, Rumeng,Zhao, Qian,Zhang, Chun
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supporting information
p. 11469 - 11472
(2020/10/12)
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- Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes
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A family of single-component iron precatalysts for the [4+4]-cyclodimerization and intermolecular cross-[4+4]-cycloaddition of monosubstituted 1,3-dienes is described. Cyclooctadiene products were obtained with high regioselectivity, and catalyst-controlled access to either cis- or trans-diastereomers was achieved using 4-substituted diene substrates. Reactions conducted either with single-component precatalysts or with iron dihalide complexes activated in situ proved compatible with common organic functional groups and were applied on multigram scale (up to >100 g). Catalytically relevant, S = 1 iron complexes bearing 2-(imino)pyridine ligands, (RPI)FeL2 (RPI = [2-(2,6-R2-C6H3-Na-CMe)-C5H4N] where R = iPr or Me, L2 = bis-olefin), were characterized by single-crystal X-ray diffraction, M??bauer spectroscopy, magnetic measurements, and DFT calculations. The structural and spectroscopic parameters are consistent with an electronic structure description comprised of a high spin iron(I) center (SFe = 3/2) engaged in antiferromagnetically coupling with a ligand radical anion (SPI = -1/2). Mechanistic studies conducted with these single-component precatalysts, including kinetic analyses, 12C/13C isotope effect measurements, and in situ M??bauer spectroscopy, support a mechanism involving oxidative cyclization of two dienes that determines regio- and diastereoselectivity. Topographic steric maps derived from crystallographic data provided insights into the basis for the catalyst control through stereoselective oxidative cyclization and subsequent, stereospecific allyl-isomerization and C-C bond-forming reductive elimination.
- Kennedy, C. Rose,Zhong, Hongyu,MacAulay, Rachel L.,Chirik, Paul J.
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supporting information
p. 8557 - 8573
(2019/06/04)
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- Corrigendum: Up the Hill: Selective Double-Bond Isomerization of Terminal 1,3-Dienes towards Z-1,3-Dienes or 2Z,4E-Dienes (Angewandte Chemie International Edition, (2012), 51, 5, (1270-1273), 10.1002/anie.201107512)
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Several years ago the authors reported an isomerisation of E-1,3-dienes by a cobalt catalyst into Z-1,3-dienes in this Communication (Scheme —original scheme). Scheme (Figure presented.) Double bond isomerisation for the stereoselective generation of Z-4
- Pünner, Florian,Schmidt, Anastasia,Hilt, Gerhard
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p. 17103 - 17103
(2019/11/21)
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- Rhodium-Catalyzed Annulations of 1,3-Dienes and Salicylaldehydes/2-Hydroxybenzyl Alcohols Promoted by 2-Ethylacrolein
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A rhodium-catalyzed 2-ethylacrolein-promoted protocol enables the annulation reactions of 1,3-dienes with either salicylaldehydes or 2-hydroxybenzyl alcohols leading to 2-alkylchroman-4-ones with high regioselectivity. This research highlights the use of 2-ethylacrolein which probably serves as a tool of bidentate coordination to rhodium intermediates. Mechanistic studies reveal that the transformation proceeds through the 1,4-hydroacylation pathway to access unsaturated linear ketones with subsequent oxo-Michael addition. (Figure presented.).
- Li, Hong-Shuang,Xiong, Yang,Zhang, Guozhu
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supporting information
p. 4246 - 4251
(2018/10/02)
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- Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes with Simple Ketones
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We developed a highly regioselective addition of 1,3-dienes with simple ketones by nickel-hydride catalyst bearing DTBM-SegPhos ligand. A wide range of aromatic and aliphatic ketones directly coupled with 1,3-dienes, providing synthetically useful γ,δ-unsaturated ketones in high yield and regioselectivity. The asymmetric version of the reaction was also realized in high enantioselectivity by using novel chiral ligand DTBM-HO-BIPHEP. The utility of this hydroalkylation was demonstrated by facile product modification and enantioselective synthesis of (R)-flobufen.
- Cheng, Lei,Li, Ming-Ming,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 11627 - 11630
(2018/09/21)
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- Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
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Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compounds, and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcohols (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, respectively. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alcohol groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
- Górski, Bartosz,Basiak, Dariusz,Talko, Alicja,Basak, Tymoteusz,Mazurek, Tomasz,Barbasiewicz, Micha?
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supporting information
p. 1774 - 1784
(2018/04/27)
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- Palladium-Catalyzed Cascade Double C—N Bond Activation: A New Strategy for Aminomethylation of 1,3-Dienes with Aminals
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A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminals via double C—N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear α,β-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C—N bond to furnish a cascade double C—N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C—N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C—N bond activation of the allylic diamines.
- Qiao, Cuifang,Chen, Anrong,Gao, Bingjian,Liu, Yang,Huang, Hanmin
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supporting information
p. 929 - 933
(2018/09/22)
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- Wittig Reactions of Trialkylphosphine-derived Ylides: New Directions and Applications in Organic Synthesis
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The development of semi-stabilized, stabilized, and functionalized ylides derived from short-chain trialkylphosphines in the Wittig-type olefination reactions toward the synthesis of alkenes, including stilbenes, styrenes, and 1,3-dienes, as well as reagents for homologation reactions, are described. The methods allow easy access to alkenes with high (E)-stereoselectivity in good yield. These reactions are conducted with weak bases in aqueous media, which allows easy separation of water-soluble phosphine oxides. The development of a mild organocatalytic process for the Wittig reaction and extension toward the preparation of reporter stilbenes under biological conditions are also described. Applications toward the preparation of biologically active natural products and derivatives are discussed.
- McNulty, James,McLeod, David,Das, Priyabrata,Zepeda-Velázquez, Carlos
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p. 619 - 632
(2016/01/15)
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- Bioinspired intramolecular diels-alder reaction: A rapid access to the highly-strained cyclopropane-fused polycyclic skeleton
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A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0 2,7]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Mother nature knows best! A gold-catalyzed reaction of enynals and 1,3-dienes, giving rapid access to the highly strained benzotricyclo[3.2.1.02,7]octane skeleton, is reported (see scheme; QMD=quinodimethane). Owing to the mild reaction conditions, excellent substrate scope, and high functional-group tolerance, this system holds potential for the construction of complex molecules with the tricyclo[3.2.1.02,7]octane skeleton. Copyright
- Zhu, Shifa,Guo, Zhengjiang,Huang, Zhipeng,Jiang, Huanfeng
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supporting information
p. 2425 - 2430
(2014/03/21)
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- Chemoselective reactions of (E)-1,3-dienes: Cobalt-mediated isomerization to (z)-1,3-dienes and reactions with ethylene
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In the asymmetric hydrovinylation (HV) of an E/Z-mixture of a prototypical 1,3-diene with (S,S)-(DIOP)CoCl2 or (S,S)-(BDPP)CoCl2 catalyst in the presence of Me3Al, the (E)-isomer reacts significantly faster, leaving behind the Z-isomer intact at the end of the reaction. The presumed [LCo-H]+-intermediate, especially when L is a large-bite angle ligand, similar to DIOP and BDPP, promote an unusual isomerization of (E/Z)-mixtures of 1,3-dienes to isomerically pure Z-isomers. A mechanism that involves an intramolecular hydride addition via an [η4-(diene)(LCo-H)]+ complex, followed by p-s-p isomerization of the intermediate Co(allyl) species, is proposed for this reaction.
- Timsina, Yam N.,Biswas, Souvagya,Rajanbabu
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supporting information
p. 6215 - 6218
(2014/05/20)
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- Up the hill: Selective double-bond isomerization of terminal 1,3-dienes towards Z-1,3-dienes or 2Z,4E-dienes
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Against all odds: Two different cobalt catalyst systems led to the selective isomerization of 1,3-dienes. In the case of the [CoBr 2(py-imine)]-catalyzed reaction, the Z-1,3-diene was formed in a highly selective manner (see scheme). When the catalyst precursor [CoBr 2(dpppMe2)] was applied, a double-bond migration and selective isomerization towards the 2Z,4E-configured 2,4-dienes were observed Copyright
- Puenner, Florian,Schmidt, Anastasia,Hilt, Gerhard
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supporting information; experimental part
p. 1270 - 1273
(2012/03/26)
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- Julia-Kocienski reaction-based 1,3-diene synthesis: Aldehyde-dependent (E, E/E, Z)-selectivity
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A new modification of Julia-Kocienski olefination reaction based on the use of cation-specific chelating agents that yields 1,3-dienes with predictable (E/Z)-selectivity on newly created double bond was developed. The influence of the aldehyde structure on reaction (E/Z) selectivity is discussed and rationalized.
- Billard, Francois,Robiette, Raphael,Pospisil, Jiri
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supporting information; experimental part
p. 6358 - 6364
(2012/10/07)
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- Catalytic enantioselective 1,2-diboration of 1,3-dienes: Versatile reagents for stereoselective allylation
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More with boron: The development of catalytic enantioselective 1,2-diboration of 1,3-dienes enables a new strategy for enantioselective carbonyl allylation reactions (see scheme). These reactions occur with outstanding levels of stereoselection and can be applied to both monosubstituted and 1,1-disubstituted dienes. The carbonyl allylation reactions provide enantiomerically enriched functionalized homoallylic alcohol products. Copyright
- Kliman, Laura T.,Mlynarski, Scott N.,Ferris, Grace E.,Morken, James P.
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supporting information; experimental part
p. 521 - 524
(2012/03/11)
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- An efficient, overall [4+1] cycloadditon of 1,3-dienes and nitrene precursors
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Intermolecular cycloadditions of conjugated dienes and nitrene precursors usually produce aziridines. A generally useful method was lacking to directly provide the [4+1] cycloadducts, 3-pyrrolines. We have realized this transformation by using an uniquely active catalyst, copper(II) 1,1,1,5,5,5-hexafluoroacetylacetonate ([Cu(hfacac)2]). The method is applicable to a wide array of dienes with good yields. When 1,4-disubsituted dienes are used as substrates, good-to-excellent cis or trans selectivity can be obtained. Interestingly, the cis or trans preference depends on the nature of the substituents, rather than diene geometry. Mechanistic studies reveal that the [4+1] cycloaddition proceeds through diene aziridination and subsequent ring expansion. Among common copper catalysts, only [Cu(hfacac)2] can efficiently catalyze both steps, which explains the unique efficiency of the catalyst.
- Wu, Qiong,Hu, Jian,Ren, Xinfeng,Zhou, Jianrong
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supporting information; experimental part
p. 11553 - 11558
(2011/11/29)
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- Regioselective semihydrogenation of dienes
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A one-pot, three-step strategy for the regioselective semihydrogenation of dienes is described. This procedure uses 9-BBN-H as a temporary protective group for alkenes. Yields range from 55% to 95%, and the reaction is tolerant of a variety of common functional groups. Additionally, the final elimination step of the sequence can be replaced with a peroxide-mediated alkylborane oxidation, generating regioselectively semihydrogenated product alcohols.
- Graham, Thomas J. A.,Poole, Thomas H.,Reese, Charles N.,Goess, Brian C.
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experimental part
p. 4132 - 4138
(2011/07/07)
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- Aqueous Wittig reactions of semi-stabilized ylides. A straightforward synthesis of 1,3-dienes and 1,3,5-trienes
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A direct synthesis of 1,3-dienes and 1,3,5-trienes from the reaction of semi-stabilized ylides and a range of saturated and unsaturated aldehydes is reported in water as solvent, employing sodium hydroxide as base. The water-soluble phosphine oxide side p
- McNulty, James,Das, Priyabrata
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experimental part
p. 5737 - 5740
(2009/12/06)
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- Stereoselective synthesis of γ-substituted (Z)-allylic boranes via kinetically controlled hydroboration of allenes with 10-TMS-9-borabicyclo[3.3.2] decane
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(Chemical Equation Presented) Kinetically controlled hydroboration of allenes 8 and 14a-d with the readily accessible Soderquist borane 7, which is generated in situ from borohydride 6, constitutes a convenient and preparatively useful method for synthesi
- Kister, Jeremy,DeBaillie, Amy C.,Lira, Ricardo,Roush, William R.
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supporting information; experimental part
p. 14174 - 14175
(2010/02/16)
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- Enantio- and diastereoselective synthesis of syn-β-hydroxyallylsilanes via a chiral (Z)-γ-silylallylboronate
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syn-β-Hydroxyallylsilanes of general structure 11 and 28 are prepared in 50-86% yield and 91-95% ee (for aliphatic aldehydes; 50% ee for benzaldehyde) via the BF3-Et2O-promoted γ-silylallylboration reactions, using reagents 14 and 15.
- Lira, Ricardo,Roush, William R.
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p. 4315 - 4318
(2008/03/11)
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- Reactivity of aldehydes with semi-stabilised arsonium ylide anions: Synthesis of terminal (E)-l,3-dienes
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A study of the reactivity of semi-stabilised arsonium ylide anions in olefinalion reactions is presented. The different ylide anions were generated by the addition of nBuLi to various arsonium halide derivatives: [Ph 2As(R)R']+X , where R and R′ are methyl, allyl, prenyl or benzyl groups. By using diallyldiphenylarsonium bromide (R = R′ = allyl) an olefinationprotocol was optimised allowing the efficient transformation of aliphatic aldehydes into terminal 1,3-dienes with a high selectivity for the E isomer (E/Z ratios ranging from 90:10 to 97:3). The olefination reactions of aldehydes with dissymmetric arsonium halides (R≠R′) are very chemoselective; with arsonium ylide anions the benzyl moiety is more reactive than the allyl moiety which is much more reactive than prenyl and methyl groups. Based on the experimental results, a mechanism is proposed for the reaction.
- Habrant, Damien,Stengel, Bruno,Meunier, Stephane,Mioskowski, Charles
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p. 5433 - 5440
(2008/02/10)
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- Palladium-catalyzed and organozinc-promoted synthesis of dienes from allylic esters possessing an acyloxy or alkoxy group
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Organozinc and a Pd catalyst promoted formation of dienes from allylic esters possessing a leaving group such as acyloxy and alkoxy groups next to the allyl moiety. The reaction proceeded with high regio- and stereoselectivity when applied to secondary allylic substrates.
- Hattori, Hatsuhiko,Katsukawa, Masahiro,Kobayashi, Yuichi
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p. 5871 - 5875
(2007/10/03)
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- STEREOSELECTIVE ADDITION OF α-CHLORO ALLYLIC CHROMIUM REAGENTS TO ALDEHYDES
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Treatment of a solution of 1,1-dichloro-2-butene and benzaldehyde with CrCl2 in THF-DMF at 25 deg C for 1 h gave threo-(Z)-4-chloro-2-methyl-1-phenyl-3-buten-1-ol in 96percent yield under high stereocontrol.
- Takai, Kazuhiko,Kataoka, Yasutaka,Utimoto, Kiitiro
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p. 4389 - 4392
(2007/10/02)
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- A Practical Synthesis of 1,3-Diene Using Allyltriphenylsilane and Titanium Tetraisopropoxide
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A practical method for the stereoselective preparation of 1,3-dienes by the use of allyltriphenylsilane as a key reagent is described.
- Ikeda, Yoshihiko,Yamamoto, Hisashi
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p. 657 - 658
(2007/10/02)
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- ALKYLATION OF DIENE ALLYLIC TERTIARY AMINES WITH GRIGNARD REAGENTS. IN SITU ACTIVATION WITH ALKYL CHLOROFORMATES.
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Diene allylic tertiary amines were substituted with Grignard reagents in the presence of lithium tetrachlorocuprate and alkyl chloroformates.According to the experimental condition employed, this reaction afforded exclusively γ-alkylation products.
- Langlois, Yves,Van Bac, Nguyen,Fall, Yagamare
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p. 1009 - 1012
(2007/10/02)
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- Synthetic Implications of the Reactions of Alkali-Metal Pentadienyls with Organic Electrophiles and Comments on the Nature of "Organopotassiums" Derived Using Lochmann's Base.
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Pentadienyl anions derived by metallation of penta-1,4-diene with n-butyl-lithium, or of penta-1,3-diene with n-butyl-lithium - potassium tert-butoxide, react with electrophiles to produce mixtures of E- and Z-5-substituted penta-1,3-dienes and 3-substituted penta-1,4-dienes.The proportions depend, amongst other things, upon the nature of the electrophile.For simple aldehydes and ketones, for example, the proportions can vary, under otherwise identical conditions, from entirely 5-substituted product (as an E/Z mixture) with benzophenone, to predominantly (64percent) 3-substituted product with acetone.Reaction with bromocyclopentane produces almost entirely the 3-substituted product.The synthetic implications of these results are discussed.The reactions of the anions generated by the two different methods are very similar, which has prompted a discussion of the nature of the reagents, often described as organopotassiums, which are derived using Lochmann's base.
- Paget, Walter E.,Smith, Keith,Hutchings, Michael G.,Martin, Gary E.
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p. 327 - 341
(2007/10/02)
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