36383-14-9

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• 108-90-7 chlorobenzene 
• 78-92-2 iso-butanol 
• 80-40-0 ethyl ester of p-toluenesulfonic acid 
• 78-76-2 s-butyl bromide 
• 1257661-30-5 2-(2-(4-chlorophenyl)butan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
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• 21758-20-3 1-(but-1-en-2-yl)-4-chlorobenzene 
• 106-39-8 bromochlorobenzene 
• 598-30-1 sec.-butyllithium 

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• 13075-05-3 1,2,3,4,5-pentabromo-6-chlorobenzene 
• 74-11-3 para-chlorobenzoic acid 

Relevant academic research and scientific papers

Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins

Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure-reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an IrII-H bond dissociation free energy around 44 kcal mol-1, which is formed after reductive 3MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer. This journal is

Bioinspired Metal-Free Formal Decarbonylation of α-Branched Aliphatic Aldehydes at Ambient Temperature

A sequence of a Baeyer–Villiger oxidation and a Lewis acid-promoted reduction of the resulting formate with Et3SiH enabled the metal-free formal decarbonylation of tertiary and secondary aliphatic aldehydes. The new methodology mimics the biosynthetic decarbonylation pathway through oxidative C?C bond cleavage rather than the C(O)?H bond activation known from conventional Tsuji–Wilkinson-type reactions. The substrate scope is complementary to existing transition-metal-catalyzed protocols.

Murahashi Cross-Coupling at ?78 °C: A One-Pot Procedure for Sequential C?C/C?C, C?C/C?N, and C?C/C?S Cross-Coupling of Bromo-Chloro-Arenes

The coupling of organolithium reagents, including strongly hindered examples, at cryogenic temperatures (as low as ?78 °C) has been achieved with high-reactivity Pd-NHC catalysts. A temperature-dependent chemoselectivity trigger has been developed for the selective coupling of aryl bromides in the presence of chlorides. Building on this, a one-pot, sequential coupling strategy is presented for the rapid construction of advanced building blocks. Importantly, one-shot addition of alkyllithium compounds to Pd cross-coupling reactions has been achieved, eliminating the need for slow addition by syringe pump.

Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer

Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.

Palladium-catalysed direct cross-coupling of secondary alkyllithium reagents

Palladium-catalysed cross-coupling of secondary C(sp3) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or the formation of reduction products. Based on our recently developed catalytic C-C bond formation with organolithium reagents, herein we present a Pd-catalysed cross-coupling of secondary alkyllithium reagents with aryl and alkenyl bromides. The reaction proceeds at room temperature and on short timescales with high selectivity and yields. This methodology is also applicable to hindered aryl bromides, which are a major challenge in the field of metal catalysed cross-coupling reactions.

Direct catalytic cross-coupling of organolithium compounds

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

Microwave-assisted silica-supported aluminum chloride-catalyzed Friedel-Crafts alkylation

Microwave irradiation is a popular method in organic synthesis to achieve high yields in shorter reaction times. This decreases total 'man-hours' in a synthetic setting. Another technique used in organic chemistry to decrease manual manipulations, is solid support reagents. The benefits of this approach is that upon completion of a reaction, a simple filtration can be performed which expedites the work-up and also produces less organic waste. Friedel-Crafts alkylation has been explored using microwave chemistry as well as with solid-supported reagents. In comparison with traditional heating, as well as with AlCl3, superior yields were observed with silica-gel bound aluminum chloride (Si-AlClx) when microwave irradiated for only 5 min.

Protodeboronation of tertiary boronic esters: Asymmetric synthesis of tertiary alkyl stereogenic centers

While tertiary boranes undergo efficient protodeboronation with carboxylic acids, tertiary boronic esters do not. Instead, we have discovered that CsF with 1.1 equiv of H2O (on tertiary diarylalkyl boronic esters) or TBAF?3H2O (on tertiary aryldialkyl boronic esters) effect highly efficient protodeboronation of tertiary boronic esters with essentially complete retention of configuration. Furthermore, substituting D2O for H2O provides ready access to deuterium-labeled enantioenriched tertiary alkanes. The methodology has been applied to a short synthesis of the sesquiterpene, (S)-turmerone.

Iron oxide nanoparticles grown on carboxy-functionalized graphite: An efficient reusable catalyst for alkylation of arenes

Here we report a simple procedure for the synthesis of a novel hybrid catalyst by growing iron oxide nanoparticles on carboxy-functionalized graphite. This hybrid catalyst demonstrated superior catalytic activity towards the alkylation of arenes with alkyl halides in contrast to commercial graphite or unsupported iron oxide nanoparticles in terms of yields and general applicability. The catalyst can be reused up to five times with a minimal loss of catalytic activity. Georg Thieme Verlag Stuttgart.

Zr-catalyzed coupling reaction of alkyl halides, tosylates, and sulfates with β-phenethyl Grignard reagents via styrene-zirconate intermediates

β-Phenethylmagnesium chlorides react with alkyl halides, tosylates, and sulfates in the presence of a catalytic amount of Cp2ZrCl 2 to afford 2-arylalkanes via alkylation of styrene-zirconate intermediates at the benzylic position. Competitive reaction using mixtures of alkyl halides (alkyl-X; X = F, Cl, Br) showed that the reactivities of the halides increase in the order of alkyl-Cl alkyl-F alkyl-Br with the relative rates of 1:19:428. Georg Thieme Verlag Stuttgart.