915703-81-0Relevant articles and documents
A Combined Experimental/Computational Study of the Mechanism of a Palladium-Catalyzed Bora-Negishi Reaction
Campos, Jesús,Nova, Ainara,Kolychev, Eugene L.,Aldridge, Simon
, p. 12655 - 12667 (2017/09/18)
Experimental and computational efforts are reported which illuminate the mechanism of a novel boron version of the widespread Negishi coupling reaction that offers a new protocol for the formation of aryl/acyl C?B bonds using a bulky boryl fragment. The role of nucleophilic borylzinc reagents in the reduction of the PdII pre-catalysts to Pd0 active species has been demonstrated. The non-innocent behavior of the PPh3 ligands of the [Pd(PPh3)2Cl2] pre-catalyst under activation conditions has been probed both experimentally and computationally, revealing the formation of a trimetallic Pd species bearing bridging phosphide (PPh2?) ligands. Our studies also reveal the monoligated formulation of the Pd0 active species, which led us to synthesize related (η3-indenyl)Pd-monophosphine catalysts which show improved catalytic performances under mild conditions. A complete mechanistic proposal to aid future catalyst developments is provided.
Chemistry of boryllithium: Synthesis, structure, and reactivity
Segawa, Yasutomo,Suzuki, Yuta,Yamashita, Makoto,Nozaki, Kyoko
, p. 16069 - 16079 (2009/05/15)
A series of lithium salts of boryl anion, boryllithiums, were synthesized and characterized by NMR spectroscopy and crystallographic analysis. In addition to the parent boryllithium compound 35a, structural modification of boryllithium, using saturated C-C and benzannulated C=C backbones in the five-membered ring and mesityl groups on the nitrogen atoms, also allowed generation of the corresponding boryllithium. The solid state structures of boryllithium showed that the boron-lithium bond is polarized where the boron atom is anionic in all (35a?DME)2, 35a?(THF)2, 35b?(THF)2, and 35c?(THF)2 when compared to the structures of hydroborane 38a-c and optimized free boryl anion opt-46a-c. Dissolution of the isolated single crystals of (35a?DME)2 and 35a?(THF)2 in THF-d8 showed that the boron-lithium bond remained in solution and free DME or THF molecules were observed. Temperature-dependent 11B NMR chemical shift changes of 35a were observed in THF-d8 or methylcyclohexane-d14, suggesting a change of chemical shift anisotropy around the boron center. The HOMO of opt-35a?(THF)2 had a lone pair character on the boron atom, as observed for phenyllithium, whereas the HOMO of hydroborane 38a corresponds to the π-orbital of the boron-containing five-membered heterocycle. The polarity of the B-Li bond, estimated by AIM analysis, was similar to that of alkyllithium. Boryllithiums 35a and 35b behave as a base or a boron nucleophile in reaction with organic electrophiles via deprotonation, SN2-type substitution, halogen-metal exchange or electron-transfer, 1,2-addition to a carbonyl group, and SNAr reaction. In the case of the reaction with CO2, intramolecular cyclization followed by CO elimination from borylcarboxylate anion and subsequent protonation gave hydroxyboranes 64a and 64b. The characters of the carbonyl groups in the borylcarbonyl compounds 60a, 60b, 61, 62, and 63a, which were obtained from the reaction of boryllithiums 35a and 35b, were investigated by X-ray crystallography, IR, and 13C NMR spectroscopy to show that the boryl substituent weakened the C=O bond when compared to carbon substituted analogues.
