4110-77-4Relevant academic research and scientific papers
Determination of the photolytic decomposition pathways of benzylchlorodiazirine by C60 probe technique
Ishitsuka, Midori O.,Enoki, Haruka,Nikawa, Hidefumi,Wakahara, Takatsugu,Tsuchiya, Takahiro,Akasaka, Takeshi,Liu, Michael T.H.
, p. 859 - 861 (2007)
By employing C60 as a chemical probe, the photolysis of benzylchlorodiazirine has been proposed to form carbene and the rearranged products via the excited state.
Kinetics of the 1,5-Dipolar Cyclization of 2-Vinylpyridinium Ylides to Indolizines. Determination of Rate Parameters by Laser Flash Photolysis
Liu, Michael T. H.,Romashin, Yuri N.,Bonneau, Roland
, p. 1179 - 1184 (1994)
Nanosecond laser flash photolysis (λ = 355 nm) of an aqueous solution of 3-chloro-3-p-chlorophenyldiazirine in isooctane produces a transient absorption at 310 nm due to the formation of the carbene. In the presence of 2-vinylpyridine, a second transient with a broad absorption band peaking at 520 nm grows in. This absorption is attributed to 2-vinylpyridinium ylide. The ylide decays with a lifetime equal to 33 μs at 25 deg C independent of the concentration of 2-vinylpyridine. As the ylide decays, there is a concomitant growth of an absorption at 330 nm, attributed to the formation of indolizine. The activation parameters for the 1,5-dipolar cyclization of the ylide to indolizine were determined; Ea = 12.1 kcal mol-1 and log A = 13.4.
Benzylchlorocarbene: Origins of Arrhenius Curvature in the Kinetics of the 1,2-H Shift Rearrangement
Merrer, Dina C.,Moss, Robert A.,Liu, Michael T.H.,Banks,Ingold, Keith U.
, p. 3010 - 3016 (1998)
Benzylchlorocarbene (1, BCC) was generated photochemically from benzylchlorodiazirine (2) in isooctane, methylcyclohexane (MCH), and tetrachloroethane (TCE) at temperatures from ～30 to -75°C. At -70°C in isooctane, the identified products included Z/E-β-chlorostyrenes 4 (46.6%), α-chlorostyrene 5 (2.4%), l,1-dichloro-2-phenylethane 6 (1.9%), a BCC-isooctane insertion product 8 (5.5%), carbene dimers 9 (3.8%), and azine 3 (30%). The significant incursion of intermolecular products 3, 8, and 9 implies that laser flash photolytic (LFP) kinetic data for the decay of BCC obtained at low temperature is biased and should not be employed in Arrhenius analyses. Accordingly, previously obtained curved Arrhenius correlations for BCC do not necessarily implicate , quantum mechanical tunneling (QMT) in the 1,2-H shift rearrangement of BCC to 4. Similarly in MCH, where BCC affords a solvent insertion product in ～44-53% yield, the curved Arrhenius correlation (Figure 1) cannot be readily interpreted. In polar solvents such as TCE, clean H-shift reactions of BCC are obtained even at -71°C; an Arrhenius correlation of LFP kinetic data is linear from 3 to -71°C (Figure 2), affording Ea = 3.2 kcal mol-1 and log A = 10.0 s-1. Therefore, QMT does not appear to play a major role in the 1,2-H shift rearrangement of BCC at ambient or near ambient temperature in solution.
Energy Barrier for 1,2-Hydrogen Migration in Benzylchlorocarbene
Liu, Michael T. H.
, p. 982 - 984 (1985)
The intermolecular-intramolecular rate constants derived from the thermolysis and photolysis of 3-chloro-3-benzyldiazirine in tetramethylene gave an excellent Arrhenius plot; an activation energy of 6.4 kcal mol-1 (26.8 kJ mol-1) was obtained for the 1,2-H migration in benzylchlorocarbene.
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
Rhodium-Catalyzed Deoxygenation and Borylation of Ketones: A Combined Experimental and Theoretical Investigation
Tao, Lei,Guo, Xueying,Li, Jie,Li, Ruoling,Lin, Zhenyang,Zhao, Wanxiang
, p. 18118 - 18127 (2020/11/26)
The rhodium-catalyzed deoxygenation and borylation of ketones with B2pin2 have been developed, leading to efficient formation of alkenes, vinylboronates, and vinyldiboronates. These reactions feature mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes via boron enolate intermediates, and the subsequent Rh-catalyzed dehydrogenative borylation of alkenes leads to the formation of vinylboronates and diboration products, which is also supported by density functional theory calculations.
Shelf-Stable (E)- A nd (Z)-Vinyl-λ3-chlorane: A Stereospecific Hyper-vinylating Agent
Kanazawa, Junichiro,Miyamoto, Kazunori,Takagi, Taisei,Uchiyama, Masanobu,Watanabe, Yuichiro
supporting information, p. 3469 - 3473 (2020/04/30)
We report the first stereoselective synthesis of stable (E)- A nd (Z)-β-chlorovinyl-λ3-chlorane via direct mesitylation of 1,2-dichloroethylene with mesityldiazonium tetrakis(pentafluorophenyl)borate under mild reaction conditions. The structure of the (E)-vinyl-λ3-chlorane was established by single-crystal X-ray analysis. Because of the enormously high leaving group ability of the aryl-λ3-chloranyl group, vinyl-λ3-chloranes undergo not only SNVσ-type reaction with extremely weak nucleophiles such as perfluoroalkanesulfonate, iodobenzene, and aromatic hydrocarbons but also coupling with phenylcopper(I) species.
Iron-Catalyzed Cross-Coupling of Alkynyl and Styrenyl Chlorides with Alkyl Grignard Reagents in Batch and Flow
Deng, Yuchao,Wei, Xiao-Jing,Wang, Xiao,Sun, Yuhan,No?l, Timothy
supporting information, p. 14532 - 14535 (2019/11/21)
Transition-metal-catalyzed cross-coupling chemistry can be regarded as one of the most powerful protocols to construct carbon–carbon bonds. While the field is still dominated by palladium catalysis, there is an increasing interest to develop protocols that utilize cheaper and more sustainable metal sources. Herein, we report a selective, practical, and fast iron-based cross-coupling reaction that enables the formation of Csp?Csp3 and Csp2?Csp3 bonds. In a telescoped flow process, the reaction can be combined with the Grignard reagent synthesis. Moreover, flow allows the use of a supporting ligand to be avoided without eroding the reaction selectivity.
AgSbF6-Catalyzed: Anti -Markovnikov hydroboration of terminal alkynes
Mamidala, Ramesh,Pandey, Vipin K.,Rit, Arnab
, p. 989 - 992 (2019/01/23)
AgSbF6-Catalyzed anti-Markovnikov addition of pinacolborane (HBpin) to terminal alkynes to produce the E-vinylboronates is reported. This efficient methodology is scalable, compatible with sterically and electronically diverse alkynes, and works at room temperature under solvent-free condition. The utility of this method is demonstrated in the facile synthesis of the clinically important (E)-2,4,3′,5′-tetramethoxystilbene.
Continuous Flow Chlorination of Alkenyl Iodides Promoted by Copper Tubing
Nitelet, Antoine,Kairouz, Vanessa,Lebel, Hélène,Charette, André B.,Evano, Gwilherm
, p. 251 - 257 (2019/01/04)
A simple continuous flow synthesis of alkenyl chlorides from the corresponding readily available alkenyl iodides in copper reactor tubing is described. A variety of alkenyl chlorides were obtained in good to excellent yields with full retention of the dou
