4110-77-4Relevant articles and documents
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.
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.
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
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.