Skeletal Transformation of Unactivated Arenes Enabled by a Low-Temperature Dearomative (3 + 2) Cycloaddition.

Simple aromatic compounds like benzene are abundant feedstocks, for which the preparation of derivatives chiefly begins with electrophilic substitution reactions or, less frequently, reductions. Their high stability makes them particularly reluctant to participate in cycloadditions under ordinary reaction conditions. Here, we demonstrate the exceptional ability of 1,3-diaza-2-azoniaallene cations to undergo formal (3 + 2) cycloadditions with unactivated benzene derivatives below room temperature, providing thermally stable dearomatized adducts on a multi-gram scale. The cycloaddition, which tolerates polar functional groups, activates the ring toward further elaboration. On treatment with dienophiles, the cycloadducts undergo a (4 + 2) cycloaddition-cycloreversion cascade to yield substituted or fused arenes, including naphthalene derivatives. The overall sequence results in the transmutation of arenes through an exchange of the ring carbons: a two-carbon fragment from the original aromatic ring is replaced with another from the incoming dienophile, introducing an unconventional disconnection for the synthesis of ubiquitous aromatic building blocks. Applications of this two-step sequence to the preparation of substituted acenes, isotopically labeled molecules, and medicinally relevant compounds are demonstrated.

Multifunctional Catalysis by a One-Dimensional Copper(II) Metal Organic Framework Containing Pre-existing Coordinatively Unsaturated Sites: Intermolecular C-N, C-O, and C-S Cross-Coupling; Stereoselective Intramolecular C-N Coupling; and Aziridination Reactions.

The coordinatively unsaturated sites (CUS) are vital in metal-centered catalysis. Metal-organic frameworks (MOFs) provide a unique opportunity to generate and stabilize CUS due to their robust structure. Generally, the generation of CUS in MOFs needs prior activation under heat and high vacuum to remove labile molecules occupying the catalytic sites. Herein, we report a solvothermal synthesis of a ready-to-use copper MOF containing accessible pre-existing CUS that does not need activation. The single crystal X-ray diffraction structure reveals a square planar Cu(II) center with two N-methylimidazoles (Mim) and one benzenedicarboxylic acid (BDC) with the formula unit [CuII(BDC)(Mim)2]n (Cu-1D) forming an infinite one-dimensional (1D) chain along the c axis. The 1D chains are stabilized by noncovalent π-π, CH···π, and H-bonding interaction to give 2D (sheet-like) and 3D networks in the solid state. The quantification of non-covalent interaction is studied by Hirshfeld surface analysis, and the formation of a higher architecture in the solid state is confirmed by SEM analysis. The reported Cu-1D MOF acts as a solid heterogeneous catalyst and exhibits efficient catalytic activity in intermolecular and intramolecular cross-coupling reactions. Intermolecular C-heteroatom cross-coupling of a variety of N-heterocycles, aliphatic, aromatic, alicyclic amines and amides (C-N), phenols (C-O), and thiols (C-S) with aryl halides (halide = I, Br) was achieved with 70 to 95% yield, better than the state-of-the-art Cu-based homogenous system. The C-N coupling catalytic cycle is initiated by the in situ reduction of Cu(II) by KOH/DMSO to Cu(I) species. Subsequently, Cu(I) undergoes oxidative addition followed by reductive elimination to form a cross-coupled product. High stereoselectivity was found for the intramolecular C-N coupling reaction to give tetrahydroquinoxalines with an enantiomeric excess (ee) of more than 99%. For a broader application, Cu-1D was applied as the catalyst for the synthesis of a library of aziridines that gives yields of up to 99% with more than 93% recyclability for each cycle.

HKUST-1 Metal Organic Framework as an Efficient Dual-Function Catalyst: Aziridination and One-Pot Ring-Opening Transformation for Formation of ß-Aryl Sulfonamides with C-C, C-N, C-S, and C-O Bonds.

Metal-organic frameworks (MOFs) are extensively used in catalysis due to their robust structure, well-defined periodic reaction centers, and high porosity. We report Cu3(BTC)2·(H2O)3 (HKUST-1) as an efficient heterogeneous catalyst for aziridination of alkene and ring-opening reaction of activated aziridines. Furthermore, we demonstrate that the transfer of a nitrogen group from PhINTs to olefins and its analogue to give aziridines takes place at the coordinatively unsaturated Cu(II) site of Cu3(BTC)2-MOF; however, the ring opening of activated aziridines is controlled by the Cu(II) Lewis acid site, and generation of coordinative unsaturation by thermal activation of the MOF is not necessarily important. The key advantage of this catalytic approach is the direct formation of C-C, C-N, C-O, and C-S bonds yielding ß-aryl sulfonamide derivatives through a simultaneous aziridination ring-opening reaction of the alkene in one pot using a single catalyst.

Stereospecific Synthesis of Highly Substituted Piperazines via an One-Pot Three Component Ring-Opening Cyclization from N-Activated Aziridines, Anilines, and Propargyl Carbonates.

A simple and efficient one-pot three-component synthetic route to highly substituted and functionalizable piperazines in high yields with excellent stereoselectivity (de, ee >99%) is reported. The SN2-type ring-opening of N-activated aziridines by anilines followed by Pd-catalyzed annulation with propargyl carbonates gives rise to the final piperazine products.

Stable lead-halide perovskite quantum dots as efficient visible light photocatalysts for organic transformations.

Lead halide perovskite (LHP) based colloidal quantum dots (CQDs) have tremendous potential for photocatalysis due to their exceptional optical properties. However, their applicability in catalysis is restricted due to poor chemical stability and low recyclability. We report halide-passivated, monodisperse CsPbBr3CQDs as a stable and efficient visible-light photocatalyst for organic transformations. We demonstrate oxidative aromatization of a wide range of heterocyclic substrates including examples which are poor hydrogen transfer (HAT) reagents. Two to five-fold higher rate kinetics were observed for reactions catalyzed by CsPbBr3CQDs in comparison with bulk-type CsPbBr3 (PNCs) or conventionally synthesized CsPbBr3CQDs and other metal organic dyes (rhodamine 6G and [Ru(bpy)3]2+). Furthermore, these CQDs exhibit improved air-tolerance and photostability and in turn show a higher turnover number (TON) of 200, compared to conventionally prepared CQDs (TON = 166) and state-of-the-art bulk-type perovskite-based catalyst (TON = 177). Our study paves the way for the practical applicability of energy-level tunable, size-controlled LHP CQDs as efficient photocatalysts in organic synthesis.

DBU-Catalyzed One-Pot Synthesis of Nearly Any Metal Salt of Fatty Acid (M-FA): A Library of Metal Precursors to Semiconductor Nanocrystal Synthesis.

The metal salts of fatty acid (M-FA) are the most widely used metal precursors to colloidal semiconductor nanocrystals (NCs). They play a key role in controlling the composition, shape, and size of semiconductor NCs, and their purity is essential for attaining impeccable batch-to-batch reproducibility in the optical and electrical properties of the NCs. Herein, we report a novel, one-pot synthesis of a library of highly pure M-FAs at near-quantitative yields (up to 91%) using 1,8-diazabicyclo[5.4.0]undec-7-ene or the related nonionic/noncoordinating base as an inexpensive and ecofriendly catalyst in a green solvent medium. The method is highly general and scalable with vast academic and industrial potential. As a practical application, we also demonstrate the use of these high-quality M-FAs in the synthesis of the spectrum of colloidal semiconductor NCs (III-V, II-VI, IV-VI, I-VI, I-III-VI, and perovskite) having absorption/emission in visible to the near-infrared region.

Stereoselective Synthesis of Hexahydroimidazo[1,2-a]quinolines via SN2-Type Ring-Opening Hydroarylation-Hydroamination Cascade Cyclization of Activated Aziridines with N-Propargylanilines.

A novel synthetic approach for the construction of 1,2,3,3a,4,5-hexahydroimidazo[1,2-a]quinolines in good yields (up to 75%) with excellent stereoselectivity (dr up to 94:6, ee up to >99%) under one-pot domino ring-opening cyclization (DROC) conditions has been developed. The DROC protocol proceeds through a Lewis acid catalyzed SN2-type ring-opening of activated aziridines with N-propargylanilines followed by intramolecular cyclization comprising concomitant hydroarylation and hydroamination steps in a domino fashion.

Tunable NIR-II emitting silver chalcogenide quantum dots using thio/selenourea precursors: preparation of an MRI/NIR-II multimodal imaging agent.

Aqueous-stable, Cd- and Pb-free colloidal quantum dots with fluorescence properties in the second near-infrared region (NIR-II, 1000-1400) are highly desirable for non-invasive deep-tissue optical imaging and biosensing. The low band-gap semiconductor, silver chalcogenide, offers a non-toxic and stable alternative to existing Pd, As, Hg and Cd-based NIR-II colloidal quantum dots (QDs). We report facile access to NIR-II emission windows with Ag2X (X = S, Se) QDs using easy-to-prepare thio/selenourea precursors and their analogues. The aqueous phase transfer of these QDs with a high conservation of fluorescence quantum yield (retention up to ∼90%) and colloidal stability is demonstrated. A bimodal NIR-II/MRI contrast agent with a tunable fluorescence and high T1 relaxivity of 408 mM-1 s-1 per QD (size ∼ 2.2 nm) and 990 mM-1 s-1 per QD (size ∼ 4.2 nm) has been prepared by grafting 50 and 120 monoaqua Gd(iii) complexes respectively to two differently sized Ag2S QDs. The size of the nanocrystals is crucial for tuning the Gd payload and the relaxivity.

Long-term ambient air-stable cubic CsPbBr3 perovskite quantum dots using molecular bromine.

We report unprecedented phase stability of cubic CsPbBr3 quantum dots in ambient air obtained by using Br2 as halide precursor. Mechanistic investigation reveals the decisive role of temperature-controlled in situ generated, oleylammonium halide species from molecular halogen and amine for the long term stability and emission tunability of CsPbX3 (X = Br, I) nanocrystals.

Stereoselective synthesis of 3-spiropiperidino indolenines via SN2-type ring opening of activated aziridines with 1H-indoles/Pd-catalyzed spirocyclization with propargyl carbonates.

3-Spiropiperidino indolenines have been synthesized via novel Lewis acid-catalyzed SN2-type ring opening of activated aziridines with 1H-indoles followed by Pd-catalyzed dearomative spirocyclization with propargyl carbonates in up to 88% yields. The step and pot-economic transformation comprises sequential C-C, C-N, and C-C bond forming steps generating two stereogenic centers including an all-carbon quaternary stereocenter to furnish the products in diastereomerically pure (dr >99 : 1) forms with excellent enantiomeric excess (ee up to >99%). The synthetic versatility of the strategy has been illustrated by converting the synthesized products into spirocyclic indolenine 2-piperidinones, dihydropiperidines, and 5-alkynylated piperidines.

Stereospecific Synthesis of 1,4,5,6-Tetrahydropyrimidines via Domino Ring-Opening Cyclization of Activated Aziridines with α-Acidic Isocyanides.

An expeditious synthetic route to access structurally diverse 1,4,5,6-tetrahydropyrimidines via domino ring-opening cyclization of activated aziridines with α-acidic isocyanides has been established. The transformation proceeds via Lewis acid mediated SN2-type ring opening of activated aziridines with α-carbanion of the isocyanides followed by a concomitant 6- endo- dig cyclization in a domino fashion to furnish the 1,4,5,6-tetrahydropyrimidine derivatives in excellent yields (up to 84%) and also in diastereo- and enantiomerically pure form (dr >99:1, ee >99%).

Syntheses of Tetrahydrobenzoazepinoindoles and Dihydrobenzodiazepinoindoles via Ring-Opening Cyclization of Activated Aziridines with 2-(2-Bromophenyl)-1H-indoles.

Two efficient, modular, step- and pot-economic strategies to access various 5,6,7,12-tetrahydrobenzo[2,3]azepino[4,5-b]indoles and 6,7-dihydro-5H-benzo[5,6][1,4]diazepino[1,7-a]indoles are disclosed that advance via SN2-type regioselective ring opening of enantiopure aziridines with 2-(2-bromophenyl)-1H-indoles at their C3 and indolyl N centers, respectively, followed by Cu-mediated C-N cyclization which furnishes the products in excellent yields with outstanding enantiomeric excesses (up to >99%).