Intramolecular carbometallation-initiated asymmetric transformations are a general and powerful approach for the construction of carbo- and heterocyclic systems with one and more stereocenters. In addition, the newly developed multiple cascade reactions are an attractive strategy for increasing the molecular complexity in one step. In recent years, great progress has been made in this area with the use of various palladium and nickel complexes with P- and N-donor chiral ligands. This review highlights recent developments in intramolecular asymmetric Heck reactions, reductive Heck reactions and various types of cascade transformations (intramolecular Heck/Heck, Heck/nucleophilic trapping, Heck/Tsuji-Trost, Heck/Suzuki-Miyaura, Heck/Sonogashira, and Heck/carbonylation) in the synthesis of complex molecules over the past 5 years. A number of examples from before 2016 are included as background information. Particular attention is paid to the use of inexpensive nickel complexes as highly efficient catalysts for a number of asymmetric reactions considered here. A perspective on current challenges and potential future developments in the field of asymmetric Heck type cyclizations is also provided.
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http://dx.doi.org/10.1039/d1ob00496d | DOI Listing |
J Am Chem Soc
December 2024
Biomolecular Mass Spectrometry and Proteomics, Bijvoet Center for Biomolecular Research and Utrecht Institute for Pharmaceutical Sciences, Utrecht University, Utrecht 3584 CH, The Netherlands.
Here, we employed a variety of mass spectrometry (MS)-based approaches, both (glyco)peptide-centric and protein-centric, to resolve the complex glycoproteoform landscape of recombinant IgA1 produced in HEK293 cells. These key immunoglobulins harbor several - and -glycosylation sites, making them considerably more heterogeneous than their IgG counterparts. We provide quantitative data on the occupancy and glycan composition for each IgA1 glycosylation site.
View Article and Find Full Text PDFOrg Lett
December 2024
Institut für Chemie, Universität Oldenburg, D-26129 Oldenburg, Germany.
Optically active spirocycles were prepared in a sequence of two palladium-catalyzed reactions. In the first step, racemic α-(-iodophenyl)-β-oxo allyl esters were submitted to the palladium-catalyzed decarboxylative asymmetric allylic alkylation reaction, furnishing the α-allylated products with a quaternary stereocenter with good yields and enantioselectivities. Subsequently, these intermediate products were converted in a Heck reaction yielding the spirocyclic structures as a mixture of - and -cyclic regioisomers.
View Article and Find Full Text PDFWe report the first asymmetric total synthesis of recently isolated heterodimeric alkaloids, narcipavlines A (1a) and B (1b), and narcikachnines A (2a) and B (2b), thereby confirming their absolute stereochemistry. These alkaloids showcase a unique heterodimeric structure, amalgamating two distinct types of alkaloids: the -hydrodibenzofuran containing tetracyclic galantamine core (6a) and the galanthindole core (7) featuring a biaryl axis. The presence of this biaryl axis, coupled with the substantial galantamine core (6a) at the substituents, imposes constraints on free rotation around the C-C axis, resulting in atropisomerism, an exceedingly rare phenomenon in nature.
View Article and Find Full Text PDFOrg Lett
December 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China.
A Pd-catalyzed asymmetric Heck cascade reaction involving the intramolecular carbopalladation of unsaturated hydrocarbons, followed by nucleophilic trapping of the resulting palladium species, is a powerful approach for constructing chiral -heterocycles. However, the use of prochiral nucleophiles in these reactions remains significantly underexplored. Herein, we report a novel Pd/Cu catalytic system for the asymmetric cascade Heck/Tsuji-Trost reaction of allenamides and aldimine esters.
View Article and Find Full Text PDFNat Commun
November 2024
Engineering Research Center of Sichuan-Tibet Traditional Medicinal Plant, College of Chemistry and Chemical Engineering, Chengdu University, Chengdu, China.
Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of a reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy has far less been investigated. Here we discover an unusual carbon-silicon-switch effect in the enantioselective construction of silicon-stereogenic center.
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