1.2.2. Davis Oxaziridines 4305 1.2.3. Metal Complexes in Enantioselective Oxidation 4305 1.3. New Applications 4307 1.3.1. Chiral Sulfinate Method 4307 1.3.2. Oxidation with Chiral Oxaziridines 4309 1.3.3. Oxidation Using Metal Complexes 4310 1.4. New Systems 4313 1.4.1. C-S Bond Formation 4314 1.4.2. Organic Oxidants 4315 1.4.3. Oxidations Catalyzed by Metal Complexes 4316 1.5. Diastereoselective Oxidations 4330 1.6. Heterogenized Systems 4332 1.7. Summary 4335 2. Biological Oxidations 4336 2.

Enantioselective synthesis of sulfoxides: 2000-2009.

The range of available arene dihydroxylating dioxygenase enzymes, their structure and mechanism, and recent examples of the application of arene cis-dihydrodiol bioproducts as chiral precursors in the synthesis of natural and unnatural products and chiral ligands are discussed.

Arene cis-dihydrodiol formation: from biology to application

Purely organic materials showing room temperature phosphorescence (RTP) and ultralong RTP (OURTP) have recently attracted much attention. However, it is challenging to integrate circularly polarized luminescence (CPL) into RTP/OURTP. Here, we show a strategy to realize CPL-active OURTP (CP-OURTP) by binding an achiral phosphor group directly to the chiral center of an ester chain. Engineering of this flexible chiral chain enables efficient chirality transfer to carbazole aggregates, resulting in strong CP-OURTP with a lifetime of over 0.6 s and dissymmetry factor of 2.3×10-3 after the conformation regulation upon photo-activation. The realized CP-OURTP is thus stable at room temperature but can be deactivated quickly at 50 °C to CP-RTP with high CPL stability during the photo-activation/thermal-deactivation cycles. Based on this extraordinary photo/thermal-responsive and highly reversible CP-OURTP/RTP, a CPL-featured lifetime-encrypted combinational logic device has been successfully established.

Stimuli-Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence.

Chiral sulfinyl compounds, sulfoxides, sulfoximines, sulfinamides, and other derivatives, play an important role in asymmetric synthesis as versatile auxiliaries, ligands, and catalysts. They are also recognized as pharmacophores found in already marketed and well-sold drugs (e.g., esomeprazole) and used in drug design. This review is devoted to the modern methods of preparation of sulfinyl derivatives in enantiopure or enantiomerically enriched form. Selected new approaches leading to racemic products for which the asymmetric variant can be developed in the future are mentioned as well.

Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds.

Synthetic supramolecular chemistry pursues not only the construction of new matter, but also control over its inherently dynamic behaviour. In this context, classic host–guest chemistry, based on the development of a myriad of macrocyclic receptors with fine-tuned affinities and selectivities, has enormously contributed to the discovery of new chemical function under self-assembly conditions. In turn, the use of molecular switches as control units within host–guest assemblies opened the door for the regulation of their dynamic interactional behaviour, which can be translated into controlled aggregation. In this review, we will focus on different strategies developed for the regulated binding of organic molecules by switchable macrocyclic hosts. As we will see, an appropriate design using stimuli-responsive versions of well-known organic receptors allows the molecular switches implemented within their structures to transform their regulated behaviour from the molecular to the supramolecular level.

Controlled binding of organic guests by stimuli-responsive macrocycles.

Molecular-logic based computation (MLBC) has grown by accumulating many examples of combinational logic gates and a few sequential variants. In spite of many inspirations being available in biology, there are virtually no examples of MLBC in chemistry where sequential and combinational operations are integrated. Here we report a simple alcohol-ketone redox interconversion which switches a macrocycle between a large or small cavity, with erect aromatic walls which create a deep hydrophobic space or with collapsed walls respectively. Small aromatic guests can be captured or released in an all or none manner upon chemical command. During capture, the fluorescence of the alcohol macrocycle is quenched via fluorescent photoinduced electron transfer switching, meaning that its occupancy state is self-indicated. This represents a chemically-driven RS Flip-Flop, one of whose outputs is fed into an INHIBIT gate. Processing of outputs from memory stores is seen in the injection of packaged neurotransmitters into synaptic clefts for onward neural signalling. Overall, capture-release phenomena from discrete supermolecules now have a Boolean basis.

https://pureadmin.qub.ac.uk/ws/files/164061776/s41467_018_07902_7.pdf

Molecular memory with downstream logic processing exemplified by switchable and self-indicating guest capture and release.

Enzyme-catalysed oxygenation and deoxygenation routes to chiral thiosulfinates

Toluene dioxygenase (TDO)-catalysed monooxygenation of methylsulfanylmethyl phenyl sulfide 1 and methylsulfanylmethyl 2-pyridyl sulfide 4, using whole cells of Pseudomonas putida UV4, occurred exclusively at the alkyl aryl sulfur centre to yield the alkyl aryl sulfoxides 2 and 5 respectively. These sulfoxides, accompanied by the dialkyl sulfoxides 3 and 6, were also obtained from naphthalene dioxygenase (NDO)-catalysed sulfoxidation of thioacetals 1 and 4 using intact cells of P. putida NCIMB 8859. Enzymatic oxidation of methyl benzyl sulfide 7, 2-phenyl-1,3-dithiane 19,
and 2-phenyl-1,3-dithiolane 23, using TDO, gave the corresponding dialkyl sulfoxides 8, 20 and 24 as minor bioproducts. TDO-catalysed dioxygenation of the alkyl benzyl sulfides 7, 15 and 17 and the thioacetals 19 and 23, with P. putida UV4, yielded the corresponding enantiopure cis-dihydrodiols 9, 16, 18, 21 and 25 as major metabolites and cis-dihydrodiol sulfoxides 14, 22 and 26 as minor metabolites, resulting from a tandem trioxygenation of substrates 7, 19 and 23 respectively. Chemical oxidation, of the enantiopure cis-dihydrodiol sulfides 9, 16, 18 and 21 with dimethyldioxirane (DMD), gave separable mixtures of the corresponding pairs of cis-dihydrodiol sulfoxide diastereoisomers 14 and 27, 28 and 29, 30 and 31, 22 and 32. While dialkyl sulfoxide bioproducts 3, 6, 20 and 24 were of variable enantiopurity (27–≥98% ee), alkyl aryl monosulfoxides 2 and 5, cis-dihydrodiols 9, 16, 18, 21 and 25 and cis-dihydrodiol sulfoxide bioproducts 14, 22 and 26 were all single
enantiomers (≥98% ee). The absolute configurations of the products, obtained from enzyme-catalysed (TDO and NDO) and chemical (DMD) oxidation methods, were determined by stereochemical correlation, circular dichroism, and X-ray crystallographic methods.

Dioxygenase-catalysed mono-, di- and tri-oxygenation of dialkyl sulfides and thioacetals: chemoenzymatic synthesis of enantiopure cis-diol sulfoxides

Dioxygenase‐Catalyzed Mono‐, Di‐, and Tri‐oxygenation of Dialkyl Sulfides and Thioacetals: Chemoenzymatic Synthesis of Enantiopure cis‐Diol Sulfoxides.

André Alves-Areias

Papers

Molecular memory with downstream logic processing exemplified by switchable and self-indicating guest capture and release.

Enzyme-catalysed oxygenation and deoxygenation routes to chiral thiosulfinates

Dioxygenase-catalysed mono-, di- and tri-oxygenation of dialkyl sulfides and thioacetals: chemoenzymatic synthesis of enantiopure cis-diol sulfoxides

Dioxygenase‐Catalyzed Mono‐, Di‐, and Tri‐oxygenation of Dialkyl Sulfides and Thioacetals: Chemoenzymatic Synthesis of Enantiopure cis‐Diol Sulfoxides.