Hexafluoroisopropan-2-ol (HFIP) has been found to be an unusually beneficial solvent for undertaking hypervalent iodine-initiated [2+2] cycloaddition of styrenes. For the initiator phenyliodine(III) diacetate (PIDA), voltammetric data demonstrate that enhanced reactivity in HFIP is due its greater oxidizing abilities this fluorinated such PIDA comparable if not superior analog bis(trifluoroacetate). These results contrast with often reported view role fluoroalcohol stabilize a radical cation...

Abstract The continuous consumption of chemical energy powers biological systems so that they can operate functional supramolecular structures. A goal modern science is to understand how simple mixtures may transition from non-living components truly emergent and the production new lifelike materials machines. In this work a replicator be maintained out-of-equilibrium by energy. system driven autocatalytic formation metastable surfactant whose breakdown products are converted back into...

The discovery of complementary methods for enantioselective transition metal-catalyzed cyclization with silyloxyenynes has been accomplished using chiral phosphine ligands. Under palladium catalysis, 1,6-silyloxyenynes bearing a terminal alkyne led to the desired five-membered ring high enantioselectivities (up 91% ee). As reactions under cationic gold 1,6- and 1,5-silyloxyenynes an internal furnished cyclopentane derivatives excellent enantiomeric excess 94% Modification substrate by...

Developing physical models of complex dynamic systems showing emergent behaviour is key to informing on persistence and replication in biology, how living matter emerges from chemistry, design with new properties. Herein we report a fully synthetic small molecule system which surfactant replicator formed two phase-separated reactants using an alkene metathesis catalyst. The self-assembles into aggregates, catalyse their own formation, thermodynamically unstable. Rather than replicating until...

Providing new methods for the selective functionalization of small molecules is highly desirable, because installing molecular diversity in a desired position, example, allows one to modulate bioactive molecules. This work reports method anilines using hexafluoroisopropanol (HFIP) as solvent promote an acid-catalyzed hydroarylation olefins. Mechanistic experiments revealed that HFIP both protonates alkene and selectively enables toward electrophilic aromatic substitution. powerful strategy...

Complementary cyclisation reactions of hex-2-ene-1,6-diamine derivatives were exploited in the synthesis alternative molecular scaffolds. The value synthetic approach was analysed using LLAMA, an open-access computational tool for assessing lead-likeness and novelty

A new method for the stereoselective synthesis of highly functionalized oxygen heterocycles using allyl or benzyl alcohols as alkylating agents is presented. The process efficient and atom economic, generating water only stoichiometric byproduct. Substoichiometric amounts Ti(OiPr)4 in HFIP solvent are key to this reactivity, tolerates a broad substitution pattern on both alcohol initiator homoallylic substrate. Preliminary mechanistic studies reveal situ formation titanium complex with which...

Abstract Reported herein is that the use of catalytic quantities hypervalent iodine reagents (phenyliodine diacetate or Dess–Martin periodinane) allows rapid and stereoselective formation cyclobutanes under very mild reaction conditions. The presence a fluorinated solvent essential for success these reactions which form unsymmetrical tri‐ tetrasubstituted through heterodimerization process involving two different alkenes.

Abstract Replication and compartmentalization are fundamental to living systems may have played important roles in life’s origins. Selection compartmentalized autocatalytic might provide a way for evolution occur life arise from non-living systems. Herein we report selection system of self-reproducing lipids where predominant species can emerge pool competitors. The lipid replicators metastable their out-of-equilibrium population be sustained by feeding the with starting materials. Phase...

A new method for the stereoselective metal-free syn-dihydroxylation of electron-rich olefins is reported, involving reaction with TEMPO/IBX in trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) and addition a suitable nucleophile. Orthogonally protected syn 1,2-diols were obtained high levels diastereocontrol, these products selectively deprotected functionalized into synthetically useful compounds.

The diastereoselective addition of lithiated vinyl sulfoxides to enantiopure sulfinimines provides direct access a wide assortment allylic sulfinamides in good yields and excellent selectivities. These adducts are key precursors differently functionalized cis- trans-dihydropyrroles. Modulation the protecting group on nitrogen prior cyclization has significant impact stereochemical outcome, allowing for selective preparation 2,5-cis- or 2,5-trans-3-sulfinyl disubstituted dihydropyrroles from...

Nitrogen containing compounds, such as anilines, are some of the most widespread and useful chemical species, although their high unselective reactivity has prevented incorporation into many interesting transformations, functionalization alkenes. Herein we report a method that allows trifluoromethylarylation alkenes using for first time, with no need additives, transition metals, photocatalysts or an excess reagents. An in-depth mechanistic study reveals key role hexafluoroisopropanol (HFIP)...

Conjugated dienes (1,3-dienes) are versatile and valuable chemical feedstocks that can be used as two-carbon or four-carbon synthons with vast applications across the industry. However, main challenge for their productive incorporation in synthetic routes is chemo-, regio-, stereoselective functionalization. Herein, we introduce a unified strategy 1,2-hydroarylation 1,4-trifluoromethylarylation of 1,3-dienes using anilines hexafluoroisopropanol. DFT calculations point toward kinetically...

The addition of enantiopure α-metalated vinyl and dienyl sulfoxides to enantiomerically pure N-sulfinimines takes place with high diastereoselectivity primarily directed by the N-sulfinimine sulfur. resulting allylic amines have been further transformed into highly functionalized 3-sulfinyl 3-sulfonyl 2,5-cis-dihydropyrroles reaction electrophiles.

Katsuki−Jacobsen oxidation−epoxidation of acyclic α-silyloxy sulfinyl dienes, followed by acid-promoted cyclization, leads to 2,5-trans-sulfonyl dihydrofurans with good selectivities. As an application, the formal syntheses (6S,7S,9R,10R)- and (6S,7S,9S,10S)-6,9-epoxynonadec-18-ene-7,10-diols is reported.

Treatment of acyclic α-hydroxy and α-tosylamino sulfinyl dienes with amines affords enantiopure 1,4-diol or 1,4-hydroxysulfonamide derivatives in good yields diastereoselectivities. This one-pot procedure entails a conjugate addition that triggers diastereoselective sulfoxide−sulfenate [2,3]-sigmatropic rearrangement.

The Overman rearrangement of allylic sulfinyl trichloroacetimidates affords trichloroacetamides with high stereoselectivity and excellent yields. Bis-allylic substrates lead to amido 2-sulfinyl butadiene derivatives in yields, total chemo- diastereoselectivity. Diels–Alder cycloaddition related dienes is controlled by the sulfoxide moiety.

Access to all-<italic>trans</italic> and <italic>trans</italic>–<italic>cis</italic>–<italic>trans</italic> cyclobutane diastereoisomers; the tether X can be cleaved.

Abstract Reported herein is that the use of catalytic quantities hypervalent iodine reagents (phenyliodine diacetate or Dess–Martin periodinane) allows rapid and stereoselective formation cyclobutanes under very mild reaction conditions. The presence a fluorinated solvent essential for success these reactions which form unsymmetrical tri‐ tetrasubstituted through heterodimerization process involving two different alkenes.