A concise and efficient method has been developed herein for the synthesis of valuable naphtho[1,2-d]imidazole derivatives. It involves an earth-abundant cobalt-catalyzed electrophilic C-H amination/cyclization/directing group removal cascade with -benzoloxyamines using paraformaldehyde as a one carbon synthon. Picolinamide has been utilized as a traceless directing group. A boosting effect of HFIP is found in the whole process. The reaction conditions are very simple and allow easy handling, making this methodology valuable and appealing.
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http://dx.doi.org/10.1039/d3cc00749a | DOI Listing |
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 PDFAcc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, 46556, USA.
Complementary methods toward the selective functionalization of indole and oxindole frameworks employing an alternative strategy in heteroaryl C-H functionalizations are presented herein. This work focuses on a catalyst-controlled, site selective C-H activation/functionalization of 3-acyl indoles, wherein an amide serves as a robust and versatile directing group capable of undergoing concomitant 1,2-acyl translocation/C-H functionalization in the presence of a Rh/Ag co-catalysts to provide the cross-coupled adducts in high yields. In contrast, the use of Ir/Ag catalysts subverted the 1,2-acyl migration to afford the corresponding C2-functionalized products in good to excellent yields.
View Article and Find Full Text PDFOrganometallics
December 2024
Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.
stabilization of known, but solution unstable, methylidene complex [Ir(Bu-PONOP)(=CH)][BAr ] allows single-crystal to single-crystal solid/gas reactivity associated with the {Ir=CH} group to be studied. Addition of H results in [Ir(Bu-PONOP)(H)][BAr ]; exposure to CO forms iridium(I) carbonyl [Ir(Bu-PONOP)(CO)][BAr ], and reaction with NH gas results in the formation of methylamine complex [(Bu-PONOP)Ir(NHMe)][BAr ] via an aminocarbene intermediate. Periodic density functional theory and electronic structure analyses confirm the Ir=CH bond character but with a very low barrier to rotation around the Ir=CH bond.
View Article and Find Full Text PDFChem Sci
December 2024
Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL) Pune 411 008 India
The isoquinoline core is present in one of the largest subsets of bioactive natural products. The multifunctional isoquinoline core exerts diverse bioactivity, resulting in the development of numerous isoquinoline-based drugs and molecules that are currently under clinical trials. We developed a new approach for phosphite-mediated [1,2] alkyl migration for an overall -C-H alkylation -alkylation of isoquinoline.
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