264144-59-4Relevant academic research and scientific papers
Palladium-Catalyzed [3 + 2] Annulation of Alkynes with Concomitant Aromatic Ring Expansion: A Concise Approach to (Pseudo)azulenes
Zhou, Fulin,Shi, Weiming,Liao, Xingrong,Yang, Yudong,Yu, Zhi-Xiang,You, Jingsong
, p. 676 - 686 (2022/01/15)
The construction of (pseudo)azulenes represents an appealing yet challenging task in organic synthetic chemistry. Herein, we disclose a palladium-catalyzed [3 + 2] annulation technique of alkynes with concomitant aromatic ring expansion driven by a diboron reagent and iodide, affording a concise approach to azulenes (7-fused-5 bicycle) and pseudoazulenes (6-fused-5 bicycle). Compared with the documented synthetic strategies, the route to (pseudo)azulenes developed herein is applicable for both homo- and cross-annulation processes and exhibits a broad substrate scope. It is worth noting that this transformation is not only suitable for the ring expansion of the phenyl moiety to afford azulenes but also applicable to the ring expansion of the electron-rich five-membered heterocycles to deliver pseudoazulenes. Experimental and computational investigations on the mechanism support the formal trans-palladium-boration across the alkyne, cis-addition of the alkyne, dearomative spiroannulation, and aromatic ring expansion process.
Cobalt-Catalyzed Hydroboration of Terminal and Internal Alkynes
González, María J.,Bauer, Felix,Breit, Bernhard
supporting information, p. 8199 - 8203 (2021/10/25)
A novel methodology to access synthetically versatile vinylboronic esters through a ligand-controlled cobalt-catalyzed hydroboration of terminal and internal alkynes is reported. The approach relies on the in situ reduction of Co(II) by H-BPin in the presence of bisphosphine ligands generating catalytically active Co(I) hydride complexes. This procedure avoids the use of stoichiometric amounts of base, and no boron-containing byproducts are generated which is translated into high functional group tolerance and atom economy.
Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights Via Experimental and Computational Studies
Mai, Binh Khanh,Nguyen, Thanh Vinh,Ton, Nhan N. H.
, p. 9117 - 9133 (2021/07/19)
Hydroboration reaction of alkynes is one of the most synthetically powerful tools to access organoboron compounds, versatile precursors for cross-coupling chemistry. This type of reaction has traditionally been mediated by transition-metal or main group catalysts. Herein, we report a novel method using tropylium salts, typically known as organic oxidants and Lewis acids, to promote the hydroboration reaction of alkynes. A broad range of vinylboranes can be easily accessed via this metal-free protocol. Similar hydroboration reactions of alkenes and epoxides can also be efficiently catalyzed by the same tropylium catalysts. Experimental studies and DFT calculations suggested that the reaction follows an uncommon mechanistic pathway, which is triggered by the hydride abstraction of pinacolborane with tropylium ion. This is followed by a series ofin situcounterion-activated substituent exchanges to generate boron intermediates that promote the hydroboration reaction.
Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes
Iakovenko, Roman,Hlavá?, Jan
supporting information, p. 440 - 446 (2021/01/28)
Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is
Zwitterion-Initiated Hydroboration of Alkynes and Styrene
Bismuto, Alessandro,Cowley, Michael J.,Thomas, Stephen P.
supporting information, p. 2382 - 2385 (2021/01/18)
The hydroboration of alkynes and styrene with HBpin has been developed using tris(pentaflurophenyl)borane (B(C6F5)3) as the initiator of catalysis. The hydroboration is proposed to be initiated by Lewis acid activation of the alkyne by (B(C6F5)3) to form a highly reactive zwitterionic species which subsequently react with HBpin to give the alkenyl boronic ester. This zwitterion has also showed potential to be a competent catalyst for the hydroboration of styrene. The zwitterionic intermediate is analogous to that proposed in the Piers borane-catalysed hydroboration and 1,1-carboboration of alkynes with B(C6F5)3. (Figure presented.).
Atroposelective Synthesis of Conjugated Diene-Based Axially Chiral Styrenes via Pd(II)-Catalyzed Thioether-Directed Alkenyl C-H Olefination
Jin, Liang,Zhang, Peng,Li, Ya,Yu, Xin,Shi, Bing-Feng
supporting information, p. 12335 - 12344 (2021/08/24)
The efficient stereoselective synthesis of conjugated dienes, especially those with axial chirality, remains a great challenge. Herein, we report the highly atroposelective synthesis of axially chiral styrenes with a conjugated 1,3-diene scaffold via a Pd(II)-catalyzed thioether-directed alkenyl C-H olefination strategy. This strategy features easy operation, mild reaction conditions, high functional group tolerance (69 examples), complete Z-selectivity, and excellent enantioselectivities (up to 99% ee). Notably, the highly enantioselective synthesis of atropisomers with two stereogenic axes were also achieved using this strategy (up to 99% ee and 97:3 dr). Moreover, the reaction could be scaled up, and the resulting axially chiral styrenes could be easily oxidized into chiral sulfoxide derivatives with high diastereoselectivities, which showed great promise as a new type of sulfur-olefin ligand.
Synthesis of Alkenylboronates from N-Tosylhydrazones through Palladium-Catalyzed Carbene Migratory Insertion
Chang, Taiwei,Huo, Jingfeng,Lei, Ming,Ping, Yifan,Wang, Jianbo,Wang, Qianyue,Wang, Rui
supporting information, p. 9769 - 9780 (2021/07/19)
The palladium-catalyzed oxidative borylation reaction of N-tosylhydrazones has been developed. The reaction features mild conditions, broad substrate scope, and good functional group tolerance. It thus represents a highly efficient and practical method for the synthesis of di-, tri-, and tetrasubstituted alkenylboronates from readily available N-tosylhydrazones. One-pot Suzuki coupling and other transformations highlight the synthetic utility of the approach. DFT calculations have revealed that palladium-carbene formation and subsequent boryl migratory insertion are the key steps in the catalytic cycle. The high stereoselectivity observed in the formation of trisubstituted alkenylboronates has been explained by distortion-interaction analysis and NBO analysis.
Copper-Photocatalyzed Hydroboration of Alkynes and Alkenes
Zhong, Mingbing,Gagné, Yohann,Hope, Taylor O.,Pannecoucke, Xavier,Frenette, Mathieu,Jubault, Philippe,Poisson, Thomas
supporting information, p. 14498 - 14503 (2021/05/21)
The photocatalytic hydroboration of alkenes and alkynes is reported. The use of newly-designed copper photocatalysts with B2Pin2 permits the formation a boryl radical, which is used for hydroboration of a large panel of alkenes and a
Regioselective Synthesis of α-Functional Stilbenes via Precise Control of Rapid cis- trans Isomerization in Flow
Lee, Hyune-Jea,Yonekura, Yuya,Kim, Nayoung,Yoshida, Jun-Ichi,Kim, Heejin
, p. 2904 - 2910 (2021/05/05)
The rapid cis-trans isomerization of α-anionic stilbene was regioselectively controlled by using flow microreactors, and its reaction with various electrophiles was conducted. The reaction time was precisely controlled within milliseconds to seconds at -50 °C to selectively give the cis- or trans-isomer in high yields. This synthetic method in flow was well-applied to synthesize precursors of commercial drug compound, (E)- and (Z)-tamoxifen with high regioselectivity and productivity.
Selective hydroboration of alkynes via multisite synergistic catalysis by PCN-222(Cu)
Ma, L. J.,Tang, Z. Y.,Yuan, J. C.,Zhang, L. J.,Zhang, X. M.
, p. 63 - 69 (2021/08/03)
Zirconium-based porphyrinic MOFs (PMOFs, MOF = metal-organic framework) have gained considerable attention in the field of electric/thermo/photo-catalysis as heterogeneous single-site catalysts; however, the study on multisite synergistic catalysis of PMO
