Laedy Sophie Pereira Perciballi’s Post

In this month’s problem session, our scientist, Vidyavathi Patro, took us through the first enantioselective total synthesis of (-)-Hunterine A which belongs to Monoterpene Indole Alkaloid (MIA) family. The authors, Elliot F. Hicks, Kengo Inoue and Brian M. Stoltz (California Institute of Technology), used an elegant aza-cope/Mannich sequence followed by azide-olefin dipolar cycloaddition to form the C7 quaternary center and the pentacyclic ring system, respectively. Here are some name reactions and key steps of the synthesis: ·       Umpolung ylide addition of cyclopentenone onto ethyl acrylate ·       Tricky 1,4-addition of the vinyl-Grignard onto the enone in which TMSCl helps promote 1,4 addition over 1,2-addition (see paper in comment section) ·       Catalytic asymmetric desymmetrisation of a meso diketone through Noyori’s transfer hydrogenation conditions ·       Beckmann rearrangement to form the piperidine ring using thionyl chloride. ·       Convergent 1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone ·       Aza-Cope/Mannich reaction and azide-olefin dipolar cycloaddition to complete the pentacyclic ring system. Aziridine formation via triazoline photolysis where degree of pyramidality of the nitrogens was a key factor of the reaction outcome.

Alpha cleavages in confined medium are not common, because typically the radical pair reforms before defusing apart. However, azido groups can be used to make alpha cleavages feasible in confined medium. Take a look at this paper in J. Org. Chem. on alpha cleavage of 2,2-diazidoIndenone in cryogenic matrices. Excellent team work Brandi James Upasana Banerjee, PhD Dushanee Sriyarathne Wandana Henarath Mohottige Benjamin Crabtree Aliz Leon Miao Hong Javeria Tariq Taha Alhayani, Pharm.D., BCPS Manabu Abe Bruce Ault https://lnkd.in/dju6wfQk

Synthesis, structural characterization, Hirshfeld surface analysis and thermal properties of dibutyltin(IV)-based complexes containing thiocyanate and pyridyl ligands Exploring New Horizons: Dibutyltin(IV) Complexes with Thiocyanate and Pyridyl Ligands 🧪🔬 Dive into the synthesis and structural characterization of novel dibutyltin(IV) complexes. Uncover insights from Hirshfeld surface analysis and examine their thermal properties. #ChemicalResearch #DibutyltinComplexes #HirshfeldSurface

✍ 📣 New Blog Post Alert!📣 ✍ ⚗ Our Senior Research Chemist Holly Bonfield has written a new blog article on Photochemical Alkene Isomerisation 💡 👩🔬 Having Holly's expertise is a real asset to the #team 👩🔬 📖 Read and download a copy here: https://lnkd.in/eqr22yAM or visit www.apexmolecular.com to read our other #blogposts #chemistrymatters #organicchemistry #synthesis #blog

We are happy to share that ChEMBL 34 is out. But wait, there is more – our ChEMBL analogs collection has been updated too! We selected compounds similar to the references from ChEMBL (Tanimoto similarity coefficient 0,6 and higher, Morgan 2 fingerprints, 1024 bit) and created ChEMBL analogs collection, now boasting over 109K compounds! Follow the link to discover more drug-like molecules: https://buff.ly/3WE5aWD #chemspace #openscience #research #science #drugdiscovery #chemicals #medicinalchemistry #drugdevelopment #chemistry #researchanddevelopment #search #chemicalindustry #science #structures

Excited to share our recent publication on JACS! Our work highlights the synergistic combination of nucleophilic addition and electrophilic functionalization strategies in tuning blue phosphorescence. Check it out from the JACS ASAP: https://lnkd.in/gPiid6e8 Special thanks to Yanyu Wu, Vinh Dang, and Chenggang Jiang for their contributions, and of course, helpful advice from our PI, Tom Teets!#JACS #Chemistry #Phosphorescence

In this elegant report, a regioselective syn-addition of Ni to alkynes followed by a 1,3-metallate shift enabled by resulting activated tetraccoordinate boron centre furnished axially chiral alkenes, which previously have been studied under 1,2-metallate shift-enabled central chirality but rarely under axial chirality protocol. This work showcases the efficient synthesis of axially chiral alkenes which otherwise highlights a major low rotational barrier and flexible framework challenge. The additional design of tailored substrates or use of expensive transition metals in this regard render the strategy unattractive. However, the strategy herein raises significant interest in tetracoordinated boron species for asymmetric construction of axially chiral alkenes, featuring late-stage functionalization, diverse substrate scope tolerance under mild condition, and synthetic applications. Enantioselectivity vs ligand percent showed a positive correlation, which means that product selectivity is highly tunable.

The authors and I are very excited to share new PLA technology through this recent publication in Macromolecules. Comparing the Structural, Thermal, and Rheological Properties of Poly(meso-lactide) to Poly(l-lactide) and Poly(rac-lactide). https://lnkd.in/gimttZP4

Cyclopropenium cations are the smallest aromatic compounds and versatile synthetic intermediates to access functionalized cyclopropenes, yet not always easy to access. The last work of Vladyslav Smyrnov now just accepted in Angewandte Chemie describes a new synthetic approach based on a photocatalyzed radical-crossover approach. https://lnkd.in/e37ZCpjR Our approach makes use of redox-active ester substituted cyclopropenes accessible in one step using the diazo compound develop in the group of Abraham Mendoza . This work is complementary to recent approaches developed by the groups of Marcos García Suero and Sidney Wilkerson-Hill. We hope our work will further contribute to make cyclopropenium cations truly versatile synthetic intermediates!

Development of a novel radical addition/aldol reaction cascade led to the first total synthesis of Ganoapplanin containing five contiguous stereocenters, two of which are quaternary, demonstrating the validity of a late-stage oxidation strategy. by Prof. Dr. Thomas Magauer et al. https://lnkd.in/gjRJ5eQb https://lnkd.in/gdqjXEfT #totavsynthesis #oxidation #latestage