The fine-tuning of metal-phosphine-catalyzed reactions relies largely on accessing ever more precisely tuned phosphine ligands by de-novo synthesis. Late-stage CÀ H functionalization and diversification of commercial phosphines offers rapid access to entire libraries of derivatives based on privileged scaffolds. But existing routes, relying on phosphorus-directed transformations, only yield functionalization of C sp 2À H bonds in a specific position relative to phosphorus. In contrast to phosphorus-directed strategies, herein we disclose an orthogonal functionalization strategy capable of introducing a range of substituents into previously inaccessible positions on arylphosphines. The strongly coordinating phosphine group acts solely as a bystander in the sterically controlled borylation of bulky phosphines, and the resulting borylated phosphines serve as the supporting ligands for palladium during diversification through phosphine self-assisted Suzuki-Miyaura reactions.
A recently found, new ionic device called Ionic Voltage Effect Soft Triode (IVEST) was optimized, tuned and embedded into a memory application concept. The device is an electrochemical micro-cell, consisting...
Due to the high affinity of phosphines for transition metals, C−H functionalization of aryl phosphines is dominated by phosphorous‐directed reactions. Here we pair a sterically controlled borylation reaction of unprotected phosphines with phosphine self‐assisted Suzuki‐Miyaura reactions to grant ready access to libraries of functionalized phosphines with a positional selectivity that complements existing methods. More information can be found in the Research Article by C. N. Neumann et al. (DOI: 10.1002/chem.202202074).
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