Achieving site selectivity in C–H functionalization reactions is a significant challenge, especially when the target C–H bond is distant from existing functional groups.1–5 Coordination of a functional group to a metal catalyst is often a key driving force and control element in many important reactions including asymmetric hydrogenation,6 epoxidation7, 8, and lithiation9. Exploitation of this effect has led to the development of a broad range of directed C–H activation reactions.10–14 However, such C–H activation methods are limited to proximal C–H bonds, which are spatially and geometrically accessible from the directing functional group. Development of meta-selective C–H functionalizations remains a significant challenge.1–5,15–17 We recently developed a U- shaped template that can be used to overcome this constraint and have shown that it can be used to selectively activate remote meta-C–H bonds.1, 2 While this approach has proven applicable for a diverse set of substrates and catalytic transformations,3–5 the need for a covalently attached complex template is a significant drawback for synthetic applications. In this manuscript, we report an alternative approach, one that employs norbornene as a transient mediator to achieve meta-selective C–H activation with a simple and common ortho-directing group. The use of a newly developed pyridine-based ligand is crucial for relaying the palladium catalyst to the meta position by norbornene following initial ortho- C–H activation. Thus, this catalytic reaction demonstrates the feasibility of switching ortho-selectivity to meta-selectivity in C–H activation of the same substrate by catalyst control.
A conformationally flexible template for the meta-C-H olefination of benzoic acids was designed through both experimental and computational efforts. The newly designed template favors a silver-palladium heterodimer low barrier transition state, and demonstrates that it is feasible to lengthen templates so as to achieve meta-selectivity when the distance between the functional handle of the native substrate and target C-H bond decreases. Analysis of the ortho-, meta-, and para-C-H cleavage transition states determined that the new template conformation optimizes the interaction between the nitrile and palladium-silver dimer in the meta-transition state, enabling palladium to cleave meta-C-H bonds with moderate-to-good yields and generally high regioselectivity. Regioselectivity is governed exclusively by the template, and kinetic experiments reveal that there is a 4-fold increase in rate in the presence of monoprotected amino acid ligands. Using a Boltzmann distribution of all accessible C-H activation transition states, it is possible to computationally predict meta-selectivity in a number of investigated templates with reasonable accuracy. Structural and distortion energies reported may be used for the further development of templates for meta-C-H activation of hitherto unexplored arene substrates.
The tropical instability waves (TIWs) in the eastern tropical Pacific have generally been considered as surface‐intensified structures resembling the first baroclinic mode. Here, we report on the existence of subsurface‐intensified TIWs on the equator. These TIWs are primarily manifested in zonal velocities, inducing maximum velocity oscillations at 70–90 m depth with amplitudes of 0.1–0.2 m/s and periods of 5–20 days. They account for ~20% of the variance at 5‐ to 30‐day periods, with another ~50% being contributed by the surface‐intensified TIWs. These waves are most significant during the TIW seasons; they are energized in part by barotropic instabilities and usually last for 3–7 months. Via interacting with the mean flow, they can induce strong out‐of‐phase shear changes between ~50‐m depth and just above the Equatorial Undercurrent core and may lead to complex diapycnal mixing structures. Their horizontal structures, generation mechanism(s), and large‐scale impacts remain to be disclosed.
With triethylamine as a vinylene source, a convenient protocol for the regioselective synthesis of β,γ-nonsubstituted 2arylquinolines from aldehydes and arylamines has been accomplished. The deaminative cyclization is also extended to long-chain tertiary alkylamines, enabling diverse alkyl groups to be concurrently installed into the pyridine rings. This process demonstrates a new conversion pathway for the simultaneous dual C(sp 3 )−H bond functionalization of tertiary amines, wherein the transient acyclic enamines generated in situ undergo the Povarov reaction.
A fungal pigment, hypocrellin D (1), together with three known perylenequinone derivatives hypocrellin A (2), B (3) and C (4), was isolated from the fruiting bodies of Shiraia bambusicola. Its structure was elucidated on the basis of spectral data including 2D NMR experiments. Hypocrellin D (1) significantly inhibited the growth of tumor cell lines Bel-7721, A-549 and Anip-973 with IC 50 values of 1.8, 8.8, 38.4 mg/ml, respectively.
A novel and efficient
entrance to the pyrimidine skeleton has been
presented via the α,β-dehydrogenation and deamination
of tertiary alkylamines. This I2-catalyzed dehydrogenative
multicomponent procedure utilizes simple aldehydes to trap the hidden
enamine intermediates and suspend generation of azadienes from amidines,
enabling the difunctionalization of a vicinal C(sp3)–H
bond. These studies provide valuable possibilities for the introduction
of aliphatic substituents and show how to switch to a new reactive
modality.
Four new natural products possessing vibralactone skeleton, 1,5-secovibralactone (1), vibralactone B (2), vibralactone C (3) and acetylated vibralactone (4), together with known compound vibralactone (5), had been isolated from cultures of the basidiomycete Boreostereum vibrans. The structures of 1-4 were elucidated on the basis of spectroscopic methods. The absolute configuration of 1 was suggested to be S by computational methods.
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