02322nas a2200253 4500008004100000022001400041245014300055210006900198260000800267490000800275520140100283653001701684653003701701653001401738653002501752653001901777100002301796700003201819700002101851700002501872700002201897700002001919856012901939 2024 eng d a0965-174800aAminoacylase efficiently hydrolyses fatty acid amino acid conjugates of Helicoverpa armigera potentially to increase the pool of glutamine0 aAminoacylase efficiently hydrolyses fatty acid amino acid conjug cFEB0 v1653 a

One of the most prevalent bioactive molecules present in the oral secretion (OS) of lepidopteran insects is fatty acid amino acid conjugates (FACs). Insect dietary components have influence on the synthesis and retaining the pool of FACs in the OS. We noted differential and diet-specific accumulation of FACs in the OS of Helicoverpa armigera by using Liquid Chromatography-Quadrupole Time of Flight Mass Spectrometry. Interestingly, we identified FACs hydrolyzing enzyme aminoacylase (HaACY) in the OS of H. armigera through proteomic analysis. Next, we have cloned, expressed, and purified active recombinant HaACY in the bacterial system. Recombinant HaACY hydrolyzes all the six identified FACs in the OS of H. armigera larvae fed on host and non-host plants and releases respective fatty acid and glutamine. In these six FACs, fatty acid moieties vary while amino acid glutamine was common. Glutamine obtained upon hydrolysis of FACs by HaACY might serve as an amino acid pool for insect growth and development. To understand the substrate choices of HaACY, we chemically synthesized, purified, and characterized all the six FACs. Interestingly, rHaACY also shows hydrolysis of synthetic FACs into respective fatty acid and glutamine. Our results underline the importance of diet on accumulation of FACs and role of aminoacylase(s) in regulating the level of FACs and glutamine.

10aAminoacylase10aFatty acid amino acid conjugates10aGlutamine10aHelicoverpa armigera10aOral secretion1 aKallure, Gopal, S.1 aSahoo, Shubhranshu, Shekhar1 aKale, Rutuja, S.1 aBarvkar, Vitthal, T.1 aKontham, Ravindar1 aGiri, Ashok, P. uhttps://library.ncl.res.in/content/aminoacylase-efficiently-hydrolyses-fatty-acid-amino-acid-conjugates-helicoverpa-armigera01374nas a2200157 4500008004100000245009100041210006900132260000800201300001600209490000700225520080000232100002301032700002201055700002201077856011701099 2025 eng d00aAchmatowicz rearrangement-enabled unified total syntheses of (+)-passifetilactones A-C0 aAchmatowicz rearrangementenabled unified total syntheses of pass cOCT a39919-399300 v153 a

In this manuscript, we report the enantio- and diastereoselective total synthesis of three cytotoxic 2-pyrone-derived natural products passifetilactones A-C. Our strategy leverages a unified synthetic approach that originates from simple furan-based building blocks. Key transformations include the Corey-Bakshi-Shibata (CBS) reduction to access chiral furan-derived alcohol, NBS-mediated Achmatowicz rearrangement to construct the alpha-hydroxy-delta-pyrone core, followed by a highly stereoselective, iridium-catalyzed dynamic kinetic intramolecular redox isomerization to access the delta-hydroxy-alpha-pyrone framework. This streamlined route enables efficient access to passifetilactones A, B, and C in 13, 5, and 8 steps, with overall yields of 12%, 54%, and 37%, respectively.

1 aVerma, Aman, Kumar1 aJeddi, Dharmaraju1 aKontham, Ravindar uhttps://library.ncl.res.in/content/achmatowicz-rearrangement-enabled-unified-total-syntheses-passifetilactones-c01096nas a2200181 4500008004100000022001400041245017100055210006900226260000900295300001200304490000700316520036400323100002500687700002400712700002600736700002200762856013000784 2025 eng d a1359-734500aAgOTf-catalyzed cascade annulation of 5-hexyn-1-ols and aldehydes: enabling the diastereoselective synthesis of [6,6,6]-trioxa-fused ketals and hexahydro-2H-chromenes0 aAgOTfcatalyzed cascade annulation of 5hexyn1ols and aldehydes en cJAN  a973-9760 v613 a

We report the unprecedented diastereoselective synthesis of novel [6,6,6]-trioxa-fused ketals via AgOTf-catalyzed cascade annulation of 5-hexyn-1-ols (with primary or secondary hydroxyl groups) and aldehydes through a [2+2+1+1] pathway. In contrast, 5-hexyn-1-ols with tertiary hydroxyl groups yield hexahydro-2H-chromenes via a [3+1+1+1] pathway.

1 aVinodkumar, Ramavath1 aNakate, Ashwini, K.1 aKrishna, Gamidi, Rama1 aKontham, Ravindar uhttps://library.ncl.res.in/content/agotf-catalyzed-cascade-annulation-5-hexyn-1-ols-and-aldehydes-enabling-diastereoselective