| 1. |
- Kunz, Susanna, et al.
(författare)
-
Derivatization of 2,1,3-Benzothiadiazole via Regioselective C–H Functionalization and Aryne Reactivity
- 2024
-
Ingår i: Journal of Organic Chemistry. - : American Chemical Society (ACS). - 0022-3263 .- 1520-6904. ; 89:9, s. 6138-6148
-
Tidskriftsartikel (refereegranskat)abstract
- Despite growing interest in 2,1,3-benzothiadiazole (BTD) as an integral component of many functional molecules, methods for the functionalization of its benzenoid ring have remained limited, and many even simply decorated BTDs have required de novo synthesis. We show that regioselective Ir-catalyzed C–H borylation allows access to versatile 5-boryl or 4,6-diboryl BTD building blocks, which undergo functionalization at the C4, C5, C6, and C7 positions. The optimization and regioselectivity of C–H borylation are discussed. A broad reaction scope is presented, encompassing ipso substitution at the C–B bond, the first examples of ortho-directed C–H functionalization of BTD, ring closing reactions to generate fused ring systems, as well as the generation and capture reactions of novel BTD-based heteroarynes. The regioselectivity of the latter is discussed with reference to the Aryne Distortion Model.
|
|
| 2. |
- Ni, Shengjun, et al.
(författare)
-
Mechanochemical Solvent-Free Catalytic C-H Methylation
- 2021
-
Ingår i: Angewandte Chemie International Edition. - : John Wiley & Sons. - 1433-7851 .- 1521-3773. ; 60:12, s. 6660-6666
-
Tidskriftsartikel (refereegranskat)abstract
- The mechanochemical, solvent-free, highly regioselective, rhodium-catalyzed C-H methylation of (hetero)arenes is reported. The reaction shows excellent functional-group compatibility and is demonstrated to work for the late-stage C-H methylation of biologically active compounds. The method requires no external heating and benefits from considerably shorter reaction times than previous solution-based C-H methylation protocols. Additionally, the mechanochemical approach is shown to enable the efficient synthesis of organometallic complexes that are difficult to generate conventionally.
|
|
| 3. |
- Posada Urrutia, Mauricio, et al.
(författare)
-
Access to long-lived room temperature phosphorescence through auration of 2,1,3-benzothiadiazole
- 2024
-
Ingår i: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 53:12, s. 5658-5664
-
Tidskriftsartikel (refereegranskat)abstract
- A series of 2,1,3-benzothiadiazole–Au(I)–L complexes have been synthesised, structurally characterised and investigated for their photophysical properties. These are the first organometallic Au(I) complexes containing a C–Au bond on the highly electron-deficient benzothiadiazole unit. The complexes exhibit solution-phase phosphorescence at room temperature, assigned to the intrinsic triplet state of the benzothiadiazole unit that is efficently populated through its attachment to gold. Comparison with routinely reported Au(I) complexes, which include intervening alkenyl linkers, suggests that previous assignments of their phosphorescence as 1π → π*(CCR) might be incomplete. Our observations affirm that, in addition to the heavy atom effect, breaking symmetry in the involved aryl motif may be of importance in controlling the luminescence properties.
|
|
