Photoredox Catalysis by 21-Thiaporphyrins: A Green and Efficient Approach for C-N Borylation and C-H Arylation.

Photoredox catalysis provides a green and sustainable alternative for C-H activation of organic molecules that eludes harsh conditions and use of transition metals. The photocatalytic C-N borylation and C-H arylation mostly depend on the ruthenium and iridium complexes or eosin Y and the use of porphyrin catalysts is still in infancy. A series of novel 21-thiaporphyrins (A2B2 and A3B type) were synthesized having carbazole/phenothiazine moieties at their meso-positions and screened as catalysts for C-N borylation and C-H arylation. This paper demonstrates the 21-thiaporphyrin catalyzed C-N borylation and het-arylation of anilines under visible light. The method utilizes only 0.1 mol % of 21-thiaporphyrin catalyst under blue light for the direct C-N borylation and het-arylation reactions. A variety of substituted anilines were used as source for expensive and unstable aryl diazonium salts in the reactions. The heterobiaryls and aryl boronic esters were obtained in decent yields (up to 88 %). Versatility of the 21-thiaporphyrin catalyst was tested by thiolation and selenylation of anilines under similar conditions. Mechanistic insight was obtained from DFT studies, suggesting that 21-thiaporphyrin undergo an oxidative quenching pathway. The photoredox process catalyzed by 21-thiaporphyrins offers a mild, efficient and metal-free alternative for the formation of C-C, C-S, and C-Se bonds in aryl compounds; it can also be extended to borylation reaction.

Quantum rotational dynamics of l-C4(3Σ-g) by H2 at low temperatures employing a machine learning augmented potential energy surface.

A new four dimensional (4D) ab initio potential energy surface (PES) is generated for the collision of C4(3Σg-) with H2(1Σg), considering both molecules as rigid rotors. A supervised neural network model is created to augment the ab initio PES and to get the missing data points. Furthermore, space fixed expansion of the augmented PES is carried out using a least squares fit over two spherical harmonics terms, resulting in radial coefficients (λ1, λ2, and λ). The centre of symmetry in both C4 and H2 forces λ1 and λ2 to have even values, respectively. Moreover, the rotational states of C4 are only populated by odd levels due to its ground state triplet symmetry and the nuclear spin (I = 0) of 12C. The cross-sections and rate coefficients with para and ortho H2 partners are studied for various odd state transitions, where the rate coefficients of the ortho are 10-20% higher than those of the latter. The de-excitation rates obtained by the para H2 collisions are also compared to those of He and are found to be ∼1.7-2.8 times the He rates, across various order transitions. The simple scaling of He rates using a factor of 1.38 proves insufficient to describe para H2 rates. Therefore, these results show the importance of explicitly studying H2 as an important colliding partner, governing the kinetics of various rotational processes in the interstellar space.

Rotational dynamics of CNCN by p-H2 and o-H2 collision at interstellar temperatures.

The rotational dynamics of isocyanogen (CNCN) is studied for its collision with para (p-) and ortho (o-) hydrogen (H2) in the temperature range of 1-100 K. These temperatures correspond to the cold dense molecular clouds in the interstellar medium where molecular hydrogen is the primary collider. An ab initio 4D potential energy surface (PES) is constructed keeping the two molecules under rigid rotor approximation. The PES is generated using the CCSD(T)-F12b/AVTZ level of theory. The 4D PES is further fitted into a neural network (NN) model, which can augment the surface and account for missing data points within spectroscopic accuracy. This NN-fitted PES is then expanded over a bispherical harmonics function to get radial terms, which are expressed into analytic functions. Thereafter, the cross sections (σ) are computed for rotational transitions of CNCN (j → j') using the close-coupling and centrifugal sudden methods for both p-H2 (jc = 0) and o-H2 (jc = 1) collision till 194 cm-1. In addition, p-H2 (jc = 0, 2) cross sections are also computed using the centrifugal sudden approximation method. The collisional rates are achieved by taking the Boltzmann distribution of σ over the translational energy of H2 till 100 K. Finally, the CNCN-H2 rates are compared to CNCN-He and NCCN-H2 collisional rates. Comparing even and odd transitions for the CNCN-H2 rates show a propensity toward higher rates for even transitions especially for o-H2 collisions considering low-order transitions.

Sulfonyl Diazaborine 'Click' Chemistry Enables Rapid and Efficient Bioorthogonal Labeling.

Finding an ideal bioorthogonal reaction that responds to a wide range of biological queries and applications is of great interest in biomedical applications. Rapid diazaborine (DAB) formation in water by the reactions of ortho-carbonyl phenylboronic acid with α-nucleophiles is an attractive conjugation module. Nevertheless, these conjugation reactions demand to satisfy stringent criteria for bioorthogonal applications. Here we show that widely used sulfonyl hydrazide (SHz) offers a stable DAB conjugate by combining with ortho-carbonyl phenylboronic acid at physiological pH, competent for an optimal biorthogonal reaction. Remarkably, the reaction conversion is quantitative and rapid (k2 >103  M-1 s-1 ) at low micromolar concentrations, and it preserves comparable efficacy in a complex biological milieu. DFT calculations support that SHz facilitates DAB formation via the most stable hydrazone intermediate and the lowest energy transition state compared to other biocompatible α-nucleophiles. This conjugation is extremely efficient on living cell surfaces, enabling compelling pretargeted imaging and peptide delivery. We anticipate this work will permit addressing a wide range of cell biology queries and drug discovery platforms exploiting commercially available sulfonyl hydrazide fluorophores and derivatives.

4D potential energy surface of NCCN-H2 collision: Rotational dynamics by p-H2 and o-H2 at interstellar temperatures.

The rotational excitation rates of NCCN species are studied for its collision with hydrogen (H2) in temperatures ranging from 1 to 100 K. Such collisions can occur in the interstellar medium with H2 in either para (p-) or ortho (o-) state, of which the p-H2 state can be approximated via its collision with He (using a scaling factor) or with a reduced rigid rotor-H2 surface (by averaging over various orientations of H2). In the current work, a four-dimensional (4D) ab initio potential energy surface (PES) is considered to study the collision dynamics of H2 in both p- and o-states and the results are compared with previous approximations. The 4D surface is constructed using the explicitly correlated coupled-cluster method CCSD(T)-F12b with the augmented triple zeta basis AVTZ and then fitted into an artificial neural networks (NN) model to augment the surface and account for missing data points. The radial coefficients are obtained from this NN fitted 4D PES via a least square fit over two spherical harmonics functions. The cross sections (σ) are computed using the close-coupling (CC) method (until 230 cm-1) for both p- and o-H2 collisions, and the rates are obtained by Boltzmann distribution over the translational energy of H2 until 100 K. The o-H2 rates are found to be higher by 25%-30% and 10%-20% compared to the p-H2 rates for Δj = 2 and higher order transitions, respectively. The coupled-state/centrifugal sudden approximated rates are also computed and found to have deviations as large as 40% when compared to CC rates, thus making quantitative descriptions unreliable.

Quantum dynamics study of rotational transitions of NCCN induced by He collision.

Quantum dynamics of the molecule cyanogen (NCCN) and its collision with helium taking place in the interstellar medium has been studied. An ab initio potential energy surface of NCCN-He, a van der Waals complex, is generated using the high-level single reference coupled-cluster with single and double and perturbative triple excitation method and aug-cc-pVQZ basis sets. Using the multipole expansion, Legendre coefficients have been calculated and utilized in determining collisional cross sections. Close-coupling calculations have been performed to study rotational excitations for He collision with NCCN. Due to nuclear spin statistics, collision induced transitions have even Δj, while odd Δj transitions are forbidden. The presence of resonances arising from rapid oscillation of cross sections in the low energy region is the result of quasi-bound states in the NCCN-He van der Waals complex. Among all the transitions, Δj = 2 are found to be predominant for excitation. Thereafter, for each transition, the rate coefficients have been calculated which decrease with increasing values of j and Δj. The result of this work will be helpful to accurately model the abundance of cyanogen in stellar atmospheres and interstellar gas.

Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes through Umpolung Reactivity of Organochlorophosphines: Phosphine Oxide-Functionalized Boron-Pendanted Compounds.

We present a novel set of frustrated Lewis pair (FLP) systems that exhibit a remarkable ability to promote the ring opening of donor-acceptor cyclopropanes (DACs). This FLP-promoted protocol offers umpolung reactivity of R1R2PCl/CN (R1, R2 = aryl, alkyl) toward DACs via nucleophilic ring-opening reactions to provide phosphinated boron-pendanted diester compounds. This novel approach exhibits the dual role of BF3·OEt2 as an activator and a reactant. The resulting compounds were found in both the keto and enol forms, with the majority being in the keto form, according to NMR analysis. The enol form was identified by single-crystal XRD analysis, and DFT calculations indicated that the keto form is more stable than the corresponding enol form.

Organocatalytic Activation of Donor-Acceptor Cyclopropanes: A Tandem (3 + 3)-Cycloaddition/Aryl Migration toward the Synthesis of Enantioenriched Tetrahydropyridazines.

An organocatalytic enantioselective (3 + 3)-cycloaddition reaction of racemic cyclopropane carbaldehydes and aryl hydrazones has been demonstrated for the first time. A wide range of enantioenriched tetrahydropyridazines with an exocyclic double bond were obtained with moderate to good yields and good to excellent enantiomeric excesses. Mechanistic investigations hinted toward a matched/mismatched kinetic resolution, and control experiments and DFT calculations unveiled that 1,3-aryl migration was concerted and intramolecular and proceeds via a four-membered transition state.