New synthesis of harzialactone A via kinetic resolution using recombinant Fusarium proliferatum lactonase

A new synthesis of harzialactone A together with its stereoisomers was achieved starting from phenyl acetone. The key step of this new route is the kinetic bioresolution of racemic cis- and trans-isomers by recombinant Escherichia coli JM109 cells expressing Fusarium proliferatum lactonase gene (reFPL). Harzialactone A was isolated in excellent ee (>99%), while moderate to good enantioselectivities (80% to >99% ee) were obtained for its isomers.     

Chiral enrichment of 2-amino-2′-hydroxy-1,1′-binaphthyl

A new synthetic procedure for the formation of 2-amino-2′-hydroxy-1,1′-binaphthyl, and a new purification procedure through the formation of Schiff bases, purification of the Schiff bases, and breakdown of the Schiff bases through amine exchange, are described. Through the new purification procedure, greater than 99% purity of the compound can be obtained easily and reliably. A set of procedures were examined to compare the efficiency and reliability to resolve 2-amino-2′-hydroxy-1,1′-binaphthyl into enantiomers. A new procedure was discovered to enrich enantiomeric excess from less than 10% to 95–99% in one step. Even a racemic mixture from an achiral procedure can be enriched to 67% e.e. in about 4% yield. The X-ray crystal structure of the racemic mixture [rhombohedral, space group Iba2, a=15.718(2) Å, b=21.703(2) Å, c=8.5398(9) Å, V=2913.2(5) ų, R1=0.0705, Z=8, d_calcd=1.301 g/cm³, F(000)=1200 e] was solved to elucidate the intriguing behavior of this compound.     

Hydroboration-oxidation of ricinoleic acid ester derivatives

The chiral center in ricinoleic acid methyl ester (ee ～100%) strongly affects the regioselectivity of its hydroboration-oxidation, so that the resulting 1,3-diol dominates by 74% over the 1,4-isomer. Furthermore, new asymmetric centers are formed preferentially with (S)-configuration, up to 87% for 1,3-diols and up to 100% for 1,4-diols.     

The organocatalytic desymmetrization of meso-ferrocene anhydride

A new and unique organocatalytic process for the desymmetrization of meso ferrocene anhydride has been developed. After optimization with a series of quinine, quinidine and squaramide ligands, the method was effective with a 60% isolated yield and 98% ee.     

Chemical Composition of the Essential Oil of the New Cultivars of Lavandula angustifolia Mill. Bred in Ukraine

Lavender, otherwise known as Lavandula angustifolia Mill., is widely used in landscaping, and its oil is a valuable raw material used in many industries. Therefore, new varieties of this plant are bred. The essential oil composition obtained from fresh flowers of thirteen new Ukrainian cultivars of L. angustifolia were analysed by GC-MS, and eighty-two components were identified. Linalool and linalyl acetate were principal constituents of all of the samples, and ranged from 11.4% to 46.7% and 7.4% to 44.2%, respectively. None of the studied samples fulfilled the requirements of Ph. Eur. and ISO 3515:2002. The main reason was a high content of α-terpineol (0.5–4.5%) and/or terpinene-4-ol (1.2–18.7%). Our results are in line with multiple researchers showing that the studied lavender oils do not comply with the industry standards despite their authenticity. We also investigated the effect of the growth year on the chemical composition of five tested cultivars grown on the same plots and noticed a considerable variability between years. The obtained experimental data did not show a significant inter-year trend for the content changes of the major components. Our results allow us to deeply characterize the new cultivars and evaluate their oil for a possible use in the industry, or to designate them for future selective breeding.     

A new type of amino amide organocatalyzed enantioselective crossed aldol reaction of ketones with aromatic aldehydes

A new type of amino amide organocatalysts was designed and synthesized from commercially available amino acids in easy steps. Their catalytic activities were examined in enantioselective crossed aldol reaction of various acyclic and cyclic ketones with aromatic aldehydes to afford the corresponding chiral anti-aldol adducts with good to excellent chemical yields, diastereoselectivities and enantioselectivities (up to 99%, up to syn:anti?=?1:99, up to 97% ee).     

Kinetic resolution of 3-hydroxycyclohexanone using different lipases

A new approach to enantiomerically enriched cyclic β-hydroxy ketones was developed. 3-Hydroxycyclohexanone was successfully resolved using lipase catalyzed transesterification. Among the lipases screened PFL, PCL, and PPL-II gave 57%, 39%, and 25% yield of the (R)-3-oxocyclohexyl acetate with 52%, 75%, and 91% ee. The PPL-II gave the highest E-value (32). The absolute configuration of the product was determined by comparison with the literature data.     

Enzymatic kinetic resolution of tropic acid

A new strategy has been developed for the CAL-B catalysed kinetic resolution of tropic acid by which both enantiomers of tropic acid can be obtained in good enantiomeric excess. (R)-Tropic acid was synthesised with 90% ee and (S)-tropic acid butyl ester in 99% ee by the hydrolysis of tropic acid butyl ester. The other enantiomers were available through the enzymatically catalysed reaction of tropic acid lactone with butanol to give (S)-tropic acid lactone and (R)-tropic acid ester in >98% ee.     

A new high-pressure phase of LiAlO2

A new high-pressure phase of LiAlO₂ has been recovered through a shock recovery technique at pressures above 9 GPa. This new phase has been refined as a tetragonal structure with lattice parameters of a=0.38866(8) nm and c=0.83001(18) nm. Its calculated density is 3.51 g/cm³, about 34% denser than γ-LiAlO₂. The aluminum and lithium cations in this new phase are six-fold coordinated, as in α-LiAlO₂ and the structure of this new phase is similar to tetragonal LiFeO₂. This new high-pressure phase is stable at temperatures up to 773 K.     

A new chiral lithium amide based on (S)-2-[1-(3,3-dimethyl)pyrrolidinylmethyl]pyrrolidine—synthesis,NMR studies and use in the enantioselective deprotonation of cyclohexene oxide

A new chiral lithium amide has been designed starting from (S)-proline. This new chiral lithium amide has been used for asymmetric deprotonation/ring opening of cyclohexene oxide to give (S)-2-cyclohexen-1-ol in 88% yield and 78% enantiomeric excess. NMR studies of the lithium amide and the ligand–substrate complex are also presented.     

Preparation of a novel biodegradable film by co-fermentation of straw and shrimp shell with Aureobasidium pullulans and Photobacterium sp. LYM-1

The green and high-value recycling of shrimp shell and straw remains a worldwide problem. This study aimed to investigate the potential utilization of a fermentation broth (FB) which contains shrimp shell and straw as a new source for preparation of biodegradable films. Aureobasidium pullulans and Photobacterium sp. LYM-1 were used in the fermentation. The cellulase activity was 115.92 U/mL and chitinase activity was 17.89 U/mL in FB. The polysaccharides concentration in FB was 1.05 mg/mL after 7 days of fermentation. An eco-friendly PVA-reinforced FB biodegradable film (FBBF) was successfully prepared and the effect of different plasticizers and surfactants on the mechanical, structural, and impermeability properties of the film was determined. The formation of new bonds between PVA and FB was proved by FTIR spectroscopy. The FBBF containing 0.25 % (w/v) glycerol and 0.01 % (v/v) tween-20 showed better strength properties. Elongation and water-swelling properties were highly improved by adding 0.2 % (m/v) citric acid. According to FE-SEM images, the smooth and tight surface of citric acid added FBBF was observed. Interestingly, the FBBF film showed good heat/moisture capacity, antifungal, and degradation properties. This report reveals a new green, and high-value recycling of straw and shrimp shell by the co-fermentation with A. pullulans and Photobacterium sp. LYM-1. It is also a novel way for the preparation of biodegradable film.     

Highly enantioselective Michael addition of ketones to nitroolefins catalyzed by (S)-pyrrolidine arenesulfonamide

A new type of catalyst for the asymmetric Michael addition reaction has been designed and synthesized. This catalyst, (S)-pyrrolidine arenesulfonamide 1, resulted in high yields (up to 93%), excellent diastereoselectivities (syn/anti ratio up to 99/1), and excellent enantioselectivities (ee up to 99%) for various cyclic ketones and nitroolefins.     

Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Optically active phosphite-type ligands with planar chirality have been synthesized for the first time. The new cymantrene-based P,N-iminodiamidophosphites demonstrated high enantioselectivity in the Pd-catalyzed allylic substitution of 1,3-diphenylallyl acetate with dimethyl malonate (up to 94% ee), pyrrolidine (up to 78% ee) and sodium para-toluene sulfinate (up to 84% ee).     

One-step synthesis of homochiral O-aryl and O-heteroaryl mandelic acids and their use as efficient 1H NMR chiral solvating agents

Job and Buchwald’s one-step copper-promoted arylation of hydroxyl groups was explored and modified so that it could be applied to the coupling of mandelic acid with several halobenzenes and haloheteroarenes. A number of new homochiral O-aryl and O-heteroaryl mandelic acids, generally presenting high enantiomeric purities, were obtained. Although yields were moderate at the best, ranging from 9% to 41%, the reaction was convenient enough to prepare new mandelic acid derivatives, some of which performed as efficient chiral solvating agents (CSAs) for the direct ¹H NMR ee value determination of several clinically and pharmacologically relevant amines.     

Synthesis of (S)-2-amino-7-methoxytetralin and isoindolo[1,2-a]isoquinolinone derivatives from l-aspartic acid

This paper describes a new total synthesis for (S)-2-amino-7-methoxytetralin, (S)-7-MeO-AT, from l-aspartic acid in an overall yield of 10% over nine steps. The major loss was ascribed to a key intramolecular Friedel–Crafts cyclization step, which afforded up to 36% yield. Attempts to perform a Friedel–Crafts cyclization of an intermediate phthalimide protected amino alcohol 13 did not give the desired protected (S)-7-MeO-AT. On the other hand, two new isoindolo[1,2-a]isoquinolinone derivatives 14 and 15, were isolated in 21 and 11% yield, respectively. The yield of 15 was improved to 70%.     

DAST promotes the synthesis of new 5-(trifluoromethyl)-3-(1,1-difluoroethan-2-yl)-1H-pyrazoles

This study describes, firstly, the synthesis of a new precursor, 4,6,6-trimethoxy-1,1,1-trifluorohex-3-en-2-one (1), from the trifluoroacetylation reaction of 1,1,3,3-tetramethoxybutane, in 65% yields. Afterwards, the reaction of 1 with two hydrazines (NH₂NHR, where R = 2-furanoyl, C₆F₅) led to a new series of 4,5-dihydro-1H-pyrazoles, containing an acetal-protected aldehyde function as substituent, in 90-97% yields. In a subsequent step, the dehydration reactions of these 4,5-dihydro-1H-pyrazoles gave the respective aromatic 1H-pyrazoles. Finally, we report the results of the deprotection reactions of the acetals to obtain the respective aldehyde function, as well as, the subsequent fluorination reaction using DAST, leading to new difluorinated derivatives in 55-60% yields.     

Synthesis of substituted carbazoles and β-carbolines by cyclization of diketoindole derivatives

A new route to substituted β-carbolines and carbazoles is described. Diketoindole intermediates, prepared by Friedel-Crafts acylations of 3-substituted indoles, have been converted to 3-hydroxycarbazoles and β-carbolines in good yields, 51-96% and 82-97%, respectively. This method also allows for the formation of 4-substituted β-carbolines. The application of this methodology to the synthesis of the natural products hyellazole and 6-chlorohyellazole is also described.     

Synthesis of two new chiral fluorous bis(oxazolines) and their applications as ligands in catalytic asymmetric reactions

Two new chiral fluorous bis(oxazolines) with a fluorous content of 56.9% and 59.3%, respectively, have been prepared starting from (S)-serine and (S)-tyrosine. Applications of these compounds as fluorous box ligands in asymmetric alkylations gave ees up to 92%, and in allylic oxidations ees up to 50%. Recycling and reuse of the ligands in asymmetric alkylation and of the catalytic system in allylic oxidation gave the same enantioselectivities.     

Asymmetric activation of tropos catalysts in the stereoselective catalytic conjugate additions of R2Zn to α,β-enones: an efficient synthesis of (−)-muscone

The preparation of a new phosphoramidite starting from (R)-BINOL and a biphenylamine is presented. In such a compound the chirality is due only to atropisomerism and this molecule possesses a flexible biphenylamine residue. Therefore it can work as a tropos catalyst. The catalytic efficiency of this new phosphoramidite has been tested in some asymmetric conjugate additions of dialkylzinc reagents to α,β-enones and compared with that of an analogous already known non-tropos ligand. Interestingly, while comparable results were obtained in the addition of ZnEt₂ to chalcone and cyclohexenone, in the case of the addition of ZnMe₂ to (E)-cyclopentadec-2-en-1-one, the new ligand provides (−)-muscone, a valuable ingredient of the perfume industry, in 84% ee, while the non-tropos ligand gives a much lower (57%) ee value.     

New and efficient RCM in pyridinic series: synthesis of 2H-dihydropyrano- or 2,3H-dihydrooxepino[3,2-b]pyridines

A new and very efficient route to polycyclic heterocycles with isosteric replacement of benzene by pyridine is reported. This strategy involving the RCM reaction in pyridinic series as a keystep allows us to prepare 2H-dihydropyrano- or 2,3H-dihydrooxepino[3,2-b]pyridines 1 and 2 in very good overall yields (47% and 44%, respectively).