This Review summarizes the advancements in Pd-catalyzed C(sp3)–H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been ...reported in the activation of alkane C–H bonds, many C(sp3)–H activation/C–C and C–heteroatom bond forming reactions have been developed by the use of directing group strategies to control regioselectivity and build structural patterns for synthetic chemistry. A number of mono- and bidentate ligands have also proven to be effective for accelerating C(sp3)–H activation directed by weakly coordinating auxiliaries, which provides great opportunities to control reactivity and selectivity (including enantioselectivity) in Pd-catalyzed C–H functionalization reactions.
C–H arylation via a Pd(II)/Pd(IV) catalytic cycle has been one of the most extensively studied C–H activation reactions since the 1990s. Despite the rapid development of this reaction in the past ...two decades, an enantioselective version has not been reported to date. Herein, we report a Pd(II)-catalyzed highly enantioselective (up to 99.5% ee) arylation of cyclopropyl C–H bonds with aryl iodides using mono-N-protected amino acid (MPAA) ligands, providing a new route for the preparation of chiral cis-aryl-cyclopropylmethylamines. The enantiocontrol is also shown to override the diastereoselectivity of chiral substrates.
The alkynylation of β-C(sp3)–H bonds in aliphatic amides with alkynyl halides has been enabled using Pd(0)/N-heterocyclic carbene (NHC) and Pd(0)/phosphine (PR3) catalysts. This is the first example ...of utilizing AlkynylPd(II)Ln complexes to activate C(sp3)–H bonds.
C–H amination of N-aryl benzamides with O-benzoyl hydroxylamines has been achieved with either Pd(II) or Pd(0) catalysts. Furthermore, we demonstrate that secondary amines can be directly used with ...benzoyl peroxide in a one-pot procedure that proceeds via the in situ generation of the appropriate O-benzoyl hydroxylamines. This catalytic reaction provides a new disconnection for the convergent synthesis of tertiary and secondary arylalkyl amines starting from benzoic acids.
Pd(II) insertion into β-methylene C(sp3)–H bonds was enabled by a mutually repulsive and electron-rich quinoline ligand. Ligand tuning led to the development of a method that allows for installation ...of an aryl group on a range of acyclic and cyclic amides containing β-methylene C(sp3)–H bonds.
We determine the low-redshift field galaxy stellar mass function (GSMF) using an area of 143 deg2 from the first three years of the Galaxy And Mass Assembly (GAMA) survey. The magnitude limits of ...this redshift survey are r < 19.4 mag over two-thirds and 19.8 mag over one-third of the area. The GSMF is determined from a sample of 5210 galaxies using a density-corrected maximum volume method. This efficiently overcomes the issue of fluctuations in the number density versus redshift. With H
0= 70 km s−1 Mpc−1, the GSMF is well described between 108 and 1011.5 M⊙ using a double Schechter function with
,
, α1=−0.35,
and α2=−1.47. This result is more robust to uncertainties in the flow-model corrected redshifts than from the shallower Sloan Digital Sky Survey main sample (r < 17.8 mag). The upturn in the GSMF is also seen directly in the i-band and K-band galaxy luminosity functions. Accurately measuring the GSMF below 108 M⊙ is possible within the GAMA survey volume but as expected requires deeper imaging data to address the contribution from low surface-brightness galaxies.
The Galaxy And Mass Assembly (GAMA) survey has obtained spectra of over 230 000 targets using the Anglo-Australian Telescope. To homogenize the redshift measurements and improve the reliability, a ...fully automatic redshift code was developed (autoz). The measurements were made using a cross-correlation method for both the absorption- and the emission-line spectra. Large deviations in the high-pass-filtered spectra are partially clipped in order to be robust against uncorrected artefacts and to reduce the weight given to single-line matches. A single figure of merit (FOM) was developed that puts all template matches on to a similar confidence scale. The redshift confidence as a function of the FOM was fitted with a tanh function using a maximum likelihood method applied to repeat observations of targets. The method could be adapted to provide robust automatic redshifts for other large galaxy redshift surveys. For the GAMA survey, there was a substantial improvement in the reliability of assigned redshifts and in the lowering of redshift uncertainties with a median velocity uncertainty of 33 km s−1.
The commonly used para‐nitrobenzenesulfonyl (nosyl) protecting group is employed to direct the CH activation of amines for the first time. An enantioselective ortho‐CH cross‐coupling between ...nosyl‐protected diarylmethylamines and arylboronic acid pinacol esters has been achieved utilizing chiral mono‐N‐protected amino acid (MPAA) ligands as a promoter.
Amine‐directed: A new enantioselective ortho‐CH cross‐coupling reaction between nosyl‐protected diarylmethylamines and arylboronic acid pinacol esters has been achieved with chiral mono‐N‐protected amino acids (MPAA) as chiral ligands. This reaction also demonstrates the feasibility of using a common protecting group to direct CH activation of amines for the first time.
Abstract
We explore constraints on the joint photometric and morphological evolution of typical low redshift galaxies as they move from the blue cloud through the green valley and on to the red ...sequence. We select Galaxy And Mass Assembly (GAMA) survey galaxies with 10.25 < log(M*/M⊙) < 10.75 and z < 0.2 classified according to their intrinsic u* − r* colour. From single component Sérsic fits, we find that the stellar mass-sensitive K-band profiles of red and green galaxy populations are very similar while g-band profiles indicate more disc-like morphologies for the green galaxies: apparent (optical) morphological differences arise primarily from radial mass-to-light ratio variations. Two-component fits show that most green galaxies have significant bulge and disc components and that the blue to red evolution is driven by colour change in the disc. Together, these strongly suggest that galaxies evolve from blue to red through secular disc fading and that a strong bulge is present prior to any decline in star formation. The relative abundance of the green population implies a typical time-scale for traversing the green valley ∼1–2 Gyr and is independent of environment, unlike that of the red and blue populations. While environment likely plays a rôle in triggering the passage across the green valley, it appears to have little effect on time taken. These results are consistent with a green valley population dominated by (early type) disc galaxies that are insufficiently supplied with gas to maintain previous levels of disc star formation, eventually attaining passive colours. No single event is needed to quench their star formation.
Finally, a choice! A highly selective palladium(II)‐catalyzed ortho‐monofluorination reaction has been achieved for the first time through a weak coordination (see scheme; ...Ar=2,3,5,6‐tetrafluoro‐4‐(trifluoromethyl)phenyl). Simple modification of this protocol allows for a choice between mono‐ and difluorination. The mono‐ and difluorinated benzoic acid derivatives are valuable in the pharmaceutical and agrochemical industries.
PDF
