Can acyclic conformational control be achieved via a sulfur-fluorine gauche effect?

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC-H) and acceptor (antibonding, σ*C-F) orbitals. This model rationalises the generic conformational preference of F-Cβ-Cα-X systems (φFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F-C-C-S(O) n ; φFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+-O-, SO2)

Improving the mesomorphic behaviour of supramolecular liquid crystals by resonance-assisted hydrogen bonding

A systematic structure-property relationship study on hydrogen-bonded liquid crystals was performed, revealing the impact of resonance-assisted hydrogen bonds (RAHBs) on the self-assembling behavior of the supramolecular architecture. The creation of a six-membered intramolecular hydrogen-bonded ring acts as a counterpart to the self-organization between hydrogen bond donators and acceptors and determines thus the suprastructure. Variation of the hydrogen-bonding pattern allowed us to significantly improve the temperature range of the reported liquid crystalline assemblies

Naturally occurring polyphenols as building blocks for supramolecular liquid crystals-substitution pattern dominates mesomorphism

A modular supramolecular approach towards hydrogen-bonded liquid crystalline assemblies based on naturally occurring polyphenols is reported. The combination of experimental observations, crystallographic studies and semi-empirical analyses of the assemblies provides insight into the structure-property relationships of these materials. Here a direct correlation of the number of donor OH-groups as well as their orientation with the mesomorphic behavior is reported. We discovered that the number and orientation of the OH-groups have a stronger influence on the mesomorphic behavior of the supramolecular assemblies than the connectivity (e.g. stilbenoid or chalconoid) of the hydrogen bond donors. Furthermore, the photo-switching behavior of selected complexes containing azopyridine ligands was investigated. This study will help future scientists to gain a deeper understanding of the underlying mechanisms and structure-property relationships of supramolecular assemblies with mesomorphic behavior, which is still one of the major challenges in current scienc

Direct Access to Unnatural Cyclobutane ?-Amino Acids through Visible Light Catalyzed [2+2]-Cycloaddition

In this work, we report the first selective, photocatalyzed [2+2]-cycloaddition of dehydroamino acids with styrene-type olefins. This simple, mild, and scalable approach relies on the use of the triplet energy transfer catalyst [Ir(dFCF(3)ppy(2))dtbpy]PF6 under visible light irradiation and provides fast access to value-added substituted strained cyclobutane alpha-amino acid derivatives. © 2022 The Authors. Published by American Chemical Society

Cyclopropene activation via I(I)/I(III) catalysis: Proof of principle and application in direct tetrafluorination

Preliminary validation of cyclopropene activation by an I(I)/I(III) catalysis manifold is disclosed to enable the direct tetrafluorination of 3,3-diarylcyclopropenes. This transformation occurs through the in situ generation of ArI(III)F2, with inexpensive iodobenzene, amine·HF complexes and Selectfluor® serving as catalyst, fluoride source and oxidant, respectively. Leveraging this approach, it has been possible to generate four C(sp3)-F bonds in a single operation (up to 44%). A Hammett study revealed that the reaction has a very narrow tolerance window with respect to the p-substituent of the aryl groups. Through a process of reaction deconstruction, a mechanism involving two discrete catalytic processes is proposed. Whereas the first cycle results in the ring opening fluorination of the 3,3-diarylcyclopropene, the second proceeds via a fluorination/phenonium ion rearrangement to liberate a tetrafluorinated diarylethane. This study adds hypervalent iodine catalysis to the plenum of strategies that facilitate cyclopropene activation

Regioselective, catalytic 1,1-difluorination of enynes

Fluorinated small molecules are prevalent across the functional small-molecule spectrum, but the scarcity of naturally occurring sources creates an opportunity for creative endeavour in developing routes to access these important materials. Iodine(I)/iodine(III) catalysis has proven to be particularly well-suited to this task, enabling abundant alkene substrates to be readily intercepted by in situ-generated λ3-iodanes and processed to high-value (di)fluorinated products. These organocatalysis paradigms often emulate metal-based processes by engaging the π bond and, in the case of styrenes, facilitating fluorinative phenonium-ion rearrangements to generate difluoromethylene units. Here we demonstrate that enynes are competent proxies for styrenes, thereby mitigating the recurrent need for aryl substituents, and enabling highly versatile homopropargylic difluorides to be generated in an operationally simple manner. The scope of the method is disclosed, together with application in target synthesis (>30 examples, up to >90% yield)

Can acyclic conformational control be achieved via a sulfur-fluorine gauche effect?

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC-H) and acceptor (antibonding, σ*C-F) orbitals. This model rationalises the generic conformational preference of F-Cβ-Cα-X systems (φFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F-C-C-S(O) n ; φFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+-O-, SO2)