Fabrication of edible nanocellulose chitosan bi-component film based on a novel "swell-permeate" approach.

The fabrication of multi-component film with colloidal particles could be inconvenient. A novel "swell-permeate" (SP) strategy was proposed to form homogeneous multi-component films. The SP strategy allows colloidal particles to fit into the polymer network by stretching the polymer chains assisted by water. We demonstrated the strategy by creating films with polysaccharide substrates as ß-cyclodextrin grafted chitosan (CS) with nanocellulose. The addition of nanocellulose significantly increased the mechanical properties and the barrier performance of the films. The size of nanocellulose particles in affecting mechanical properties was investigated by applying different length of cellulose nanocrystal (CNC), the longer of which, due to denser physical entanglements, showed a better increase to the film in the elastic modulus and tensile strength to 4.54-fold and 5.71-fold, respectively. The films were also loaded with ethyl-p-coumarate (EpCA) and had an enhanced performance in anti-microbial for Altenaria alternata, Salmonella typhi, and Escherichia coli. The anti-oxidative property was increased as well, and both effects were valid both in vitro and in ready-to-eat apples. The strategy provides a practical and convenient method for fabricating colloidal particle containing films, and the novel idea of "swell-permeate" is potentially regarded as a new solution to the challenge of ready-to-eat food quality maintenance.

Asymmetric Synthesis of Functionalized Phenylalanine Derivatives via Rh-Catalyzed Conjugate Addition and Enantioselective Protonation Cascade.

The asymmetric conjugate addition of arylboronic acids to N-phthalimidodehydroalanine 1i catalyzed by Rh(I)/L1a enables the facile preparation of chiral functionalized phenylalanines. The reaction proceeds by a conjugate addition and enantioselective protonation cascade, affording a rhodium enolate that undergoes re-face protonation. The reaction tolerates various arylboronic acids and can be used in the gram-scale synthesis of (S)-phenylalanine hydrochloride, demonstrating the reaction scope and the synthetic feasibility of the process.

Asymmetric Synthesis of ß-Aryl ß-Imido Sulfones Using Rhodium Catalysts with Chiral Diene Ligands: Synthesis of Apremilast.

A chiral rhodium(I)-diene catalyst enabled the one-step synthesis of ß-aryl ß-imido sulfones under mild reaction conditions. By selection of the chiral diene ligand L1a or L2, each enantiomer of the chiral ß-aryl ß-imido sulfone target can be accessed with high stereoselectivity. Demonstration of the scope of the reaction, which includes the synthesis of an N-protected chiral ß-amino ß-phenyl sulfone, culminated with the efficient synthesis of the heteroatom-rich active pharmaceutical ingredient apremilast.

Access to ß2-Amino Acids via Enantioselective 1,4-Arylation of ß-Nitroacrylates Catalyzed by Chiral Rhodium Catalysts.

The highly enantioselective conjugate addition of a variety of arylboronic acids to ß-nitroacrylates is reported to provide optically active α-aryl ß-nitropropionates in up to 70% yields and >99.5% ee's, which are useful building blocks for preparing chiral ß2-amino acids. The applicability of this transformation is demonstrated by converting 3aa into the ß2-amino acid 5 and transforming 3ap to ß-amino ester 7 via reduction and reductive N-alkylation. The latter compound is a precursor for preparing ent-ipatasertib.

Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A.

The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (-)-crispine A.

Planar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadienyl)manganese(I) Scaffold To Achieve High Robustness and High Enantioselectivity.

A series of 2-methyl-1,3-propenylene-bridged (η5-diarylphosphinocyclopentadienyl)(phosphine)manganese(I) dicarbonyl complexes 2 have been developed as a new class of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold, which show better robustness as well as higher enantioselectivity over phosphine-olefin ligands 1 with a planar-chiral (η6-arene)chromium(0) framework. The practical enantiospecific and scalable synthesis of 2 has been established. Phosphine-olefin ligands 2 enable construction of an effective chiral environment around a transition-metal center upon coordination, and thus their rhodium(I) complexes exhibit excellent catalytic performance in the various asymmetric addition reactions of arylboron nucleophiles. Complex 2b, which has a bis(3,5-dimethylphenyl)phosphino group on the cyclopentadienyl ring, is found to be a superior chiral ligand in the rhodium-catalyzed asymmetric 1,4-addition reactions of arylboronic acids to various cyclic/acyclic enones giving the corresponding arylation products in over 99% ee. On the other hand, 2c and 2d, which have bis[3,5-bis(trifluoromethyl)phenyl]phosphino and bis(3,5-di-tert-buthyl-4-methoxyphenyl)phosphino groups, respectively, are highly efficient chiral ligands in the rhodium-catalyzed asymmetric 1,2-addition reactions of the arylboron nucleophiles to imines or aldehydes showing up to 99.9% ee. The X-ray crystallographic studies of (R)-2b and [RhCl((S*)-2b)]2 reveal the absolute configuration of 2b and its phosphine-olefin bidentate coordination to a rhodium(I) cation. Structural comparison with [RhCl((R*)-1b)]2 postulates the origins of the higher enantioselectivity of newly developed phosphine-olefin ligands 2.

Synthesis of Quaternary-Carbon-Containing ß2,2 -Amino Acids by the RhI -Catalyzed Enantioselective Arylation of α-Substituted ß-Nitroacrylates.

An enantioselective RhI -catalyzed conjugate addition reaction of α-substituted ß-nitroacrylates with various arylboronic acids by using chiral RhI diene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted ß-nitropropionate products in up to 63 % yield and 99 % ee. Reaction of either (E)- or (Z)-ß-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated. To demonstrate the utility of the method, ethyl (R)-1,1-methyl-1-phenyl-3-nitropropionate, prepared herein, was converted to the non-proteinogenic ß2,2 -amino acid, (R)-2-(aminomethyl)-2-phenylpropanoic acid, and to the ß2,2 -lactam, (R)-3-methyl-3-phenylazetidin-2-one. In addition, a tripeptide, which comprised l-phenylalanine, l-alanine, and ß2,2 -amino acid 7, was also synthesized.