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1. Suzuki–Miyaura cross-coupling of esters by selective O–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(μ-Cl)Cl] ₂ precatalysts: catalyst evaluation and mechanism

   https://doi.org/10.1039/D1CY00312G  

   Yang, Shiyi; Zhou, Tongliang; Poater, Albert; Cavallo, Luigi; Nolan, Steven P.; Szostak, Michal (January 2021, Catalysis Science & Technology)

   null (Ed.)

   The cross-coupling of aryl esters has emerged as a powerful platform for the functionalization of otherwise inert acyl C–O bonds in chemical synthesis and catalysis. Herein, we report a combined experimental and computational study on the acyl Suzuki–Miyaura cross-coupling of aryl esters mediated by well-defined, air- and moisture-stable Pd( ii )–NHC precatalysts [Pd(NHC)(μ-Cl)Cl] 2 . We present a comprehensive evaluation of [Pd(NHC)(μ-Cl)Cl] 2 precatalysts and compare them with the present state-of-the-art [(Pd(NHC)allyl] precatalysts bearing allyl-type throw-away ligands. Most importantly, the study reveals [Pd(NHC)(μ-Cl)Cl] 2 as the most reactive precatalysts discovered to date in this reactivity manifold. The unique synthetic utility of this unconventional O–C(O) cross-coupling is highlighted in the late-stage functionalization of pharmaceuticals and sequential chemoselective cross-coupling, providing access to valuable ketone products by a catalytic mechanism involving Pd insertion into the aryl ester bond. Furthermore, we present a comprehensive study of the catalytic cycle by DFT methods. Considering the clear advantages of [Pd(NHC)(μ-Cl)Cl] 2 precatalysts on several levels, including facile one-pot synthesis, superior atom-economic profile to all other Pd( ii )–NHC catalysts, and versatile reactivity, these should be considered as the ‘first-choice’ catalysts for all routine applications in ester O–C(O) bond activation. 

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2. Sonogashira Cross-Coupling of Aryl Ammonium Salts by Selective C–N Activation Catalyzed by Air- and Moisture-Stable, Highly Active [Pd(NHC)(3-CF ₃ -An)Cl ₂ ] (An = Aniline) Precatalysts

   https://doi.org/10.1021/acs.orglett.2c02534  

   Lei, Peng; Wang, Yibo; Zhang, Caixia; Hu, Yuge; Feng, Juntao; Ma, Zhiqing; Liu, Xili; Szostak, Roman; Szostak, Michal (September 2022, Organic Letters)
3. Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl₂] Catalysts: Reaction Development, Scope, and Mechanism

   https://doi.org/10.1021/acs.joc.3c00912  

   Yang, Shiyi; Yu, Xiang; Liu, Yaxu; Tomasini, Michele; Caporaso, Lucia; Poater, Albert; Cavallo, Luigi; Cazin, Catherine_S J; Nolan, Steven P; Szostak, Michal (August 2023, The Journal of Organic Chemistry)
4. Suzuki‐Miyaura Cross‐Coupling of Amides using Well‐Defined, Air‐Stable [(PR ₃ ) ₂ Pd(II)X ₂ ] Precatalysts

   https://doi.org/10.1002/adsc.202000122  

   Ma, Siyue; Zhou, Tongliang; Li, Guangchen; Szostak, Michal (April 2020, Advanced Synthesis & Catalysis)

   Abstract A versatile method for the Suzuki‐Miyaura cross‐coupling of amides using highly active, well‐defined, and air‐stable Pd−phosphine precatalysts is reported. Most notably, the method represents the first example of using practical and operationally‐simple Pd(II)−phosphine precatalysts in the emerging amide bond cross‐coupling manifold. The reactions are efficient at 0.10 mol% loading, furnishing biaryl ketones with high chemoselectivity for N−C(O) bond cleavage. This versatile method enables for the first time to achieve Pd−phosphine‐catalyzed cross‐coupling of amides at ppm loading. This C−N cross‐coupling can be used to efficiently furnish pharmaceutical intermediates by orthogonal Pd‐catalyzed cross‐couplings. We fully expect that operationally‐simple [(PR₃)₂Pd(II)X₂] precatalysts as effective triggers for N−C(O) cross‐coupling will be of broad synthetic and catalytic interest. magnified image 

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5. Li _3.6 In ₇ S _11.8 Cl: an air- and moisture-stable superionic conductor

   https://doi.org/10.1039/d5sc01907a  

   Oyekunle, Ifeoluwa P; Truong, Erica; Poudel, Tej P; Chen, Yudan; Jin, Yongkang; Ojelade, Islamiyat A; Deck, Michael J; Ogbolu, Bright; Islam, Md Mahinur; Ojha, Pawan K; et al (January 2025, Chemical Science)

   Li_3.6In₇S_11.8Cl has a face-centered cubic arrangement of S²⁻/Cl⁻stabilized by Li⁺/In³⁺that form 3D ion conduction paths. The moisture stability and fast ion conduction make Li_3.6In₇S_11.8Cl a promising electrolyte for solid-state batteries. 

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