F:Highly flammable;
592-42-7Relevant articles and documents
Reactions of Allyl Chloride on Ag(110) To Form η3-C3H5 and 1,5-Hexadiene
Carter, Robert N.,Anton, A. Brad,Apai, G.
, p. 4410 - 4411 (1992)
-
Bauld
, p. 859 (1962)
Swift et al.
, p. 212 (1971)
Extrinsic precursor-assisted synthesis of 1,5-hexadiene on Cu(100)
Celio,Scheer,White
, p. 2990 - 2996 (2001)
The reaction between allyl bromide and previously chemisorbed η3-allyl to form 1,5-hexadiene on Cu(100) at cryogenic temperatures has been examined using reflection absorption infrared spectroscopy and temperature-programmed desorption. Above 110 K, the 1,5-hexadiene formation rate decreases with increasing temperature and is controlled by the residence time of dosed allyl bromide, whereas below 100 K, the rate increases with temperature and is controlled by the reaction of weakly adsorbed allyl bromide with chemisorbed η3-allyl. Above 110 K, a precursor state model is used to interpret the data. The activation energy difference, Ed-Er, between desorption and reaction of allyl bromide with η3-allyl is 12 kJ mol-1.
Reaktion von (1,4-Diazabutadien)bis(alken)nickel(0)-Komplexen mit Ethin
Bonrath, Werner,Michaelis, Stephan,Poerschke, Klaus R.,Gabor, Barbara,Mynott, Richard,Krueger, Carl
, p. 255 - 260 (1990)
The (1,4-diazabutadiene)bis(alkene)nickel(0) complexes iPr2Ph)2-dad>Ni(C2H4)2 iPr2Ph)2-dad = 2,6iPr2C6H3-N=CHCH=N-C6H3-2,6iPr2> (1) and iPr2Ph)2-dad>Ni(η2,η2-C6H10) (2) react with ethyne above - 100 deg C (1) or -30 deg C (2) with coupling of two ethyne molecules to afford the dinuclear complex iPr2Ph)2-dad>Ni>2(C4H4) (3) which contains a ferrol-type nickelacyclopentadiene-nickel(O) bonding element.A single-crystal X-ray structure study of 3 revealed strongly distorted coordination geometries of the nickel centers, which are also present in solution at low temperature (1H, 13C-NMR).At higher temperatures dynamic processes take place by which the coordinative distortions at the nickel centers are reversed and the bonding situations of the nickel atoms are exchanged.However, a rotation of the phenyl groups around the N-C bonds can be excluded.Similarly, Ni>2(C4H4) (4) has been obtained and characterized.
Srinivasan,Levi
, p. 3363 (1963)
Benn,R. et al.
, p. 103 - 112 (1978)
Reductive C(sp3)-C(sp3) homo-coupling of benzyl or allyl halides with H2using a water-soluble electron storage catalyst
Futakuchi, Sayaka,Miyazawa, Keishi,Nakai, Hidetaka,Ogo, Seiji,Shimauchi, Daiki,Takahashi, Yukina,Yatabe, Takeshi,Yoon, Ki-Seok
, p. 39450 - 39454 (2021/12/27)
This paper reports the first example of a reductive C(sp3)-C(sp3) homo-coupling of benzyl/allyl halides in aqueous solution by using H2as an electron source {turnover numbers (TONs) = 0.5-2.3 for 12 h}. This homo-coupling reaction, promoted by visible light, is catalysed by a water-soluble electron storage catalyst (ESC). The reaction mechanism, and four requirements to make it possible, are also described.
Mild olefin formationviabio-inspired vitamin B12photocatalysis
Bam, Radha,Pollatos, Alexandros S.,Moser, Austin J.,West, Julian G.
, p. 1736 - 1744 (2021/02/22)
Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B12-dependent photoreceptor CarH, where photolysis of a cobalt-carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B12-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B12to be a powerful platform for developing mild olefin-forming reactions.
The Synthesis of Chiral Allyl Carbamates via Merger of Photoredox and Nickel Catalysis
Garbacz, Mateusz,Stecko, Sebastian
supporting information, p. 3213 - 3222 (2020/07/06)
A mild, and versatile, organophotoredox/Ni-mediated protocol was developed for the direct preparation of diverse, enantioenriched allyl carbamates. The reported approach represents a significant departure from classical step-by-step synthesis of allyl carbamates. This dual photoredox/Ni based strategy offers unrivalled capacity for convergent unification of readily available alkyl halides and chiral carbamates derived from 1-bromo-alken-3-ols with high chemoselectivity and efficiency. The reported photoredox/Ni catalyzed cross-coupling reaction is not limited to carbamates, but also to other O-derivatives such as esters, ethers, acetals, carbonates or silyl ethers. To demonstrate the utility of the reported protocol, the resulting allyl carbamates were transformed into functionalized non-racemic allylamines through a sigmatropic rearrangement reaction in enantiospecific manner. This approach allowed for synthesis of enantiomeric allylamines by a simple control of the geometry of a double bond of allyl carbamates. (Figure presented.).
