39669-95-9Relevant articles and documents
Nickel-Catalyzed Carboxylation of Conjugated Dienes with Carbon Dioxide and DIBAL-H for the Synthesis of β,γ-Unsaturated Carboxylic Acids
Luo, Ying,Chan, Bun,Fukuda, Tsutomu,Onodera, Gen,Kimura, Masanari
supporting information, p. 1551 - 1554 (2021/01/21)
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.
Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides
Li, Ming-Ming,Cheng, Lei,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
supporting information, p. 2948 - 2951 (2020/12/15)
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.
Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and beyond
Gevorgyan, Vladimir,Kurandina, Daria,Shing Cheung, Kelvin Pak,Yata, Tetsuji
supporting information, p. 9932 - 9937 (2020/06/27)
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.
Cu-Catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-dienes with CO2
Zhang, Penglin,Zhou, Zhanglang,Zhang, Rumeng,Zhao, Qian,Zhang, Chun
supporting information, p. 11469 - 11472 (2020/10/12)
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.
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)
Pünner, Florian,Schmidt, Anastasia,Hilt, Gerhard
, p. 17103 - 17103 (2019/11/21)
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
Palladium-Catalyzed Cascade Double C—N Bond Activation: A New Strategy for Aminomethylation of 1,3-Dienes with Aminals
Qiao, Cuifang,Chen, Anrong,Gao, Bingjian,Liu, Yang,Huang, Hanmin
supporting information, p. 929 - 933 (2018/09/22)
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.
Remote Nucleophilic Allylation by Allylrhodium Chain Walking
Groves, Alistair,Martínez, Jose I.,Smith, Joshua J.,Lam, Hon Wai
, p. 13432 - 13436 (2018/09/21)
Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z-homoallylic alcohols and amines, respectively.
Palladium-Catalyzed Formal [4+2] Cycloaddition of Benzoic and Acrylic Acids with 1,3-Dienes via C—H Bond Activation: Efficient Access to 3,4-Dihydroisocoumarin and 5,6-Dihydrocoumalins
Sun, Youwen,Zhang, Guozhu
supporting information, p. 708 - 711 (2018/06/06)
We report a palladium-catalyzed formal intermolecular [4+2] cycloaddition of benzoic and acrylic acids with 1,3-dienes including the stock chemicals 1,3-butadiene and isoprene leading to synthetically useful 3,4-dihydroisocoumarins and 5,6-dihydrocoumalins. Stepwise C—H bond cleavage and annulation are likely involved in the reaction pathway. The synthetic potential of the methodology was demonstrated by two short derivatizations and total synthesis of natural product Clausamine B.
Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
Górski, Bartosz,Basiak, Dariusz,Talko, Alicja,Basak, Tymoteusz,Mazurek, Tomasz,Barbasiewicz, Micha?
supporting information, p. 1774 - 1784 (2018/04/27)
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.
Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes with Simple Ketones
Cheng, Lei,Li, Ming-Ming,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
supporting information, p. 11627 - 11630 (2018/09/21)
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.
