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A novel strategy for the organocatalytic asymmetric synthesis of spiro-δ-lactam oxindoles was developed via a [3 + 3] annulation of 3-carboxamide oxindoles and β,γ-unsaturated α-keto esters with excellent diastereoselectivities and enantioselectivities.

We report an efficient strategy that combines organic photoredox and hydrogen atom transfer to deliver

One new spirocyclic lactone, terreinlactone C (1), and one new benzopyran derivative, 2,2-dimethyl-3-hydroxychroman-6-aldehyde (2), were discovered from the fungus Aspergillus terreus. The chemical structures of compounds 1 and 2 were elucidated by detailedly analyzing NMR and HRESIMS data. Compound 1 is the first natural product with a 1-oxaspiro[4.5]decan-2-one ring system and a possible biogenetic pathway is proposed. Two compounds were tested for their cytotoxic activities against five human cancer cell lines.[Formula: see text].

A highly regioselective approach to access amide enol carbamates and carbonates 5a-5c', 7a-7h, and 9 was developed through Cu(OTf)2-catalyzed reactions of ynamides 4 with t-butyl carbamates 2 and 8 and t-butyl carbonates 6. Moreover, this strategy was successfully applied to generate amide enol carbamates 11a-11s and 14a-14f from imides 10 and 13 with ynamides through an N-Boc cleavage-addition ring-opening process. A range of substituents was amenable to this transformation, and the desired amide enol carbamates and carbonates were obtained in moderate to good yields.

A simple and efficient strategy has been established for the synthesis of δ-lactam fused oxindoles via the Michael/N-hemiketalization cascade reaction of 3-carboxamide oxindoles and α,β-unsaturated trifluoromethyl ketones. A wide range of structurally novel CF3-containing spiro-δ-lactam oxindoles featuring acyl at the ortho-position of spiro carbon atoms were obtained in moderate to good yields with excellent diastereoselectivities under mild conditions. This work represents the first example of a systematic study of 3-carboxamide oxindoles as 1,3-C,N bisnucleophiles.

An efficient method for asymmetric synthesis of epohelmins A (3), B (4) and their isomer 24 is detailed in this report. The key feature in this divergent synthesis includes the SmI2-induced cross-coupling of N-tert-butanesulfinyl imine 10 with chiral aldehyde 9 derived from d -malic acid. A cascade cyclization to the pyrrolizidine skeleton is achieved in our synthetic route for epohelmins. In addition, an interesting intramolecular oxa-Michael addition was observed for epohelmin A (3).

A convenient method for diastereoselective synthesis of the key intermediate 5 from triheterocyclic fragment and polyketide 6 for hoiamides A (1) and B (2) was developed. The main feature is the successive construction of four stereogenic centers from C33 to C36 for hoiamides A (1) through the well-established Oppolzer’s anti-aldol and Paterson’s anti-aldol methodology. Furthermore, asymmetric allylation was also utilized as a key step to form the stereogenic center at C32 for hoiamides A (1).

An efficient asymmetric approach to access functionalized pyrido- and pyrrolo[1,2- c][1,3]oxazin-1-ones has been developed through a nucleophilic addition-cyclization process of N, O-acetal with ynamides. A number of substituted ynamides 8a-8o and 3-silyloxypyrrolidine or piperidine N, O-acetals 6a, 7 were amenable to this transformation, and the desired products 9a-9o, 10a-10m were obtained with excellent regioselectivities and outstanding diastereoselectivities. Moreover, chiral ynamides 14a-14f could also experience this addition-cyclization process to afford products 15a-15f in excellent yields.

An efficient approach for asymmetric synthesis of (+)-spicigerine, (+)-cassine and their 3-epimers has been developed through the intramolecular diastereoselective tandem addition/cyclisation process of α-chiral aldimine 9 with methylmagnesium bromide and the asymmetric addition of nucleophilic reagents to aminal 14. Moreover, the first asymmetric synthesis of (+)-spicigerine has been achieved in this manuscript. In this synthetic strategy, the asymmetric syntheses of (+)-spicigerine and (+)-cassine was achieved in a 14% overall yield and nine steps and an 18% overall yield and seven steps from cheap α-chiral aldimine 9, respectively.

A diastereoselective new approach for the synthesis of trans-4-hydroxy-5-allyl-2-pyrrolidinone 9 has been developed through In-mediated allylation of α-chiral aldimine 8 with allyl bromide. The stereochemistry at the C-2 stereogenic center of 9 was controlled by both the α-OTBS substitution and the sulfinamide moiety. The utility of this asymmetric allylation is demonstrated by the asymmetric syntheses of epohelmins A (4) and B (10).

An efficient and step-economical approach to access functionalized pyrrolizidine derivatives by a one-pot tandem sequence, including an aldol condensation and subsequent 1,3-dipolar cycloaddition process, has been developed, starting from acetone, aldehyde, and proline. A number of substituted aromatic aldehydes were amenable to this transformation, and the desired products, racemic 7a–7w and chiral 9a–9m, were obtained with excellent regioselectivities and outstanding diastereoselectivities. Moreover, in situ NMR studies revealed MgSO4 could effectively promote the aldol condensation pathway in this tandem process.

In this report, the originally proposed rupestonic acid (5) and pechueloic acid (3) were efficiently synthesized. The chiral lactone 13, recycled from the degradation of saponin glycosides, was utilized to prepare the key chiral fragment 11. During the exploration of this convergent assembly strategy, the ring-closing metathesis (RCM), SmI2-prompted intermolecular addition, and [2,3]-Wittig rearrangement proved to be effective transformations for the synthesis of subunits.

Different amounts of the potent mutagenic and/or carcinogenic heterocyclic aromatic amines (HAAs) are formed in muscle-based foods under different cooking methods. HAAs (9 varieties) in lamb patties cooked using traditional Chinese cooking methods (roasting, frying, panfrying, and stewing in seasonings) were investigated. The total HAAs contents in roasted, fried, pan-fried, and stewed patties were 4.39-123.15 ng/g, 3.59-43.24 ng/g, 0.71-10.05 ng/g, and 51.07-120.32 ng/g, respectively. Amounts of HAAs increased as cooking time increased. 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP) was the dominant HAAs in deep roasted and fried samples, while 1-methyl- 9H-pyrido [3,4-b] indole (Harman) and 9H-pyrido [3,4-b] indole (Norharman) were the main HAAs in pan-fried and stewed samples. Types and contents of HAAs formed at different cooking times using different methods are unique. Stewing in seasoning generated a higher HAAs content than the high-temperature cooking methods roasting, frying, and pan-frying.

A method was established for the simultaneous determination of nine heterocyclic aromatic amines (HAAs) in mutton products by solid phase extraction-high performance liquid chromatography (SPE-HPLC). As a result, the sample was prepared by ultrasound in 2 mol/L NaOH, and dichloromethane was selected as the extraction solvent. The extract was purified and concentrated with an MCX SPE column. The chromatographic separation was achieved on a reverse-phase C18 column by gradient elution using 0.01 mol/L phosphoric acid (adjusted to pH 3.6 by triethylamine) and acetonitrile, detected with a diode array detector (DAD) at 228 nm for 2-amino-9H-pyrido [ 2,3-b] indole (AaC) and 2-amino-3-methyl-9H-pyrido [ 2,3-b] indole (MeAaC); 253 nm for 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 1-methyl-9H-pyrido[3, 4-b] indole (Harman), 9H-pyrido[3,4-b] indole (Norharman); 263 nm for 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo [4,5-f] quinoxaline (4, 8-DiMeIQx), 3-amino-1-methyl-5H-pyrido [4,3-b] indole (Trp-p-2); 321 nm for 2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine (PhIP). The results showed that the nine HAAs can be separated efficiently. The recoveries (n = 6) of the nine HAAs spiked in meat were between 50.27% and 94.77% with the relative standard deviations of 0.08%-4.42%. The limits of detection of this method were 1.6 -41.0 microg/L for the nine HAAs. The method is simple, accurate, rapid and repeatable. It can be used for the simultaneous determination of the nine HAAs in mutton products.

A series of diaryl amines, ethers and thioethers were synthesized under microwave irradiation efficiently at presence of KF/Al2O3 in 83%–96% yields without any solvent. The salient characters of this method lie in short reaction time, high yields, general applicability to substrates and simple workup procedure. At the same time, their antifungal biological activities against six phytopathogen were evaluated. Most of the compounds (3b, 3c, 3g–o) are more potent than thiophannate-methyl against to Magnaporthe oryzae. This implies that diaryl amine or ether moiety may be helpful in finding a fungicide against Magnaporthe oryzae.