Iridium catalyzed primary alcohol oxidation triggers reductive C-O bond cleavage of isoprene oxide to form aldehyde-allyliridium pairs that combine to form products of tert-(hydroxy)-prenylation, a motif found in >2000 terpenoid natural products. Curtin-Hammett effects are exploited to enforce high levels of anti-diastereo- and enantioselectivity in the formation of an all-carbon quaternary center. The present redox-triggered carbonyl additions occur in the absence of stoichiometric byproducts, premetalated reagents, and discrete alcohol-to-aldehyde redox manipulations.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4090370 | PMC |
| http://dx.doi.org/10.1021/ja504625m | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Chemodivergent dearomatization of benzene-linked O-oxime esters EnT-induced radical cross-coupling.
Chem Sci
January 2025
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology (SCUT) Guangzhou 510640 China.
Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials. Herein, we report a novel strategy by leveraging benzene-linked O-oxime esters as triply functionalized precursors to form two distinct persistent radicals under a chemodivergent pathway. These radicals then couple with a cyclohexadienyl radical for either carboamination or carbo-aminoalkylation.
View Article and Find Full Text PDFMetathesis chemistry of inorganic cumulenes driven by B-O bond formation.
Chem Sci
December 2024
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK
The reaction chemistry of an unprecedented 'inorganic cumulene' - featuring a five-atom BNBNB chain - towards C[double bond, length as m-dash]O (and related) multiple bonds is disclosed. In marked contrast to related all-carbon systems, the intrinsic polarity of the BNBNB chain (featuring electron-rich nitrogen and electron-deficient boron centres) enables metathesis chemistry with electrophilic heteroallenes such as CO and with organic carbonyl compounds. Transfer of the borylimide unit to [CO], [CS], [PP{(NDippCH)}] and [C(H)Ph] moieties generates (boryl)N[double bond, length as m-dash]C[double bond, length as m-dash]X systems (X = O, S, PP{(NDippCH)}, C(H)Ph), driven thermodynamically by B-O bond formation.
View Article and Find Full Text PDFGrowth characteristics, redox potential changes and proton motive force generation in K1 during growth on various carbon sources.
AIMS Microbiol
November 2024
Department of Biochemistry, Microbiology and Biotechnology, Faculty of Biology, Yerevan State University, 0025 Yerevan, Armenia.
Article Synopsis
- The K1 strain of an extremophile microorganism primarily uses aerobic metabolism, with some strains able to grow anaerobically depending on the carbon sources available.
- Experiments showed that the strain's growth was affected by the concentration and pH of carbon sources, notably that high glucose concentrations hindered growth while other sugars did not.
- The study discovered that K1's bioenergetic properties, including membrane potential and proton motive force, vary with different carbon sources and acidic conditions, revealing potential for biotechnological applications.
The photo-isomerization of the cyclononatetraenyl ligand and related rare earth complexes.
Chem Sci
November 2024
LCM, CNRS, Ecole Polytechnique, Institut Polytechnique de Paris Route de Saclay 91120 Palaiseau France
The cyclononatetraenyl (Cnt) ligand is a large monoanionic ligand. It is easily synthesized by ring expansion after cyclopropanation of the cyclooctatetraenyl (Cot) ligand. The Cnt ligand can be reported as the --- () isomer, where the aromatic ring is flat, and all carbon atoms form a homogenous ring, and as the --- () isomer, where one carbon places itself inside the ring.
View Article and Find Full Text PDFIron-Catalyzed Cross-Electrophile Coupling for the Formation of All-Carbon Quaternary Centers.
J Am Chem Soc
December 2024
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
Quaternary carbon centers are desirable targets for drug discovery and complex molecule synthesis, yet the synthesis of these motifs within traditional cross-coupling paradigms remains a significant challenge due to competing β-hydride elimination pathways. In contrast, the bimolecular homolytic substitution (S2) mechanism offers a unique and attractive alternative pathway. Metal porphyrin complexes have emerged as privileged catalysts owing to their ability to selectively form primary metal-alkyl complexes, thereby eliminating the challenges associated with tertiary alkyl complexation with a metal center.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!