Transmetalation of Unsaturated Carbon Nucleophiles from Boron-Containing Species to the Mid to Late d-Block Metals of Relevance to Catalytic C−X Coupling Reactions (X = C, F, N, O, Pb, S, Se, Te)

The Role of Metal Hydroxide Complexes in Late Transition Metal‐Mediated Transmetalation Reaction: The Case of Gold

“…[6] Further studies demonstrated that this methodology was also successful using a Cl precursor [7] and either sterically demanding dialkylbiarylphosphine and N-heterocyclic carbene ligands (NHC) or bulky coupling partners. [8] Subsequent investigation led the same group to demonstrate further utilities of boronic acids and esters to provide in good yields diaurated compounds. [9] This fundamental reaction is of further interest as the transmetalation reaction represents a key step in the possible role of gold in cross-coupling reactions.…”

“…Phenyltrihydroxoborate 20 reacted with 1 in a 1:1 ratio in toluene-d 8 at room temperature and afforded 3 in 1 h [Eq. (1)].…”

Palladium-catalyzed acylative cross-coupling of amides with diarylborinic acids and sodium tetraarylborates

“…Therefore, tetraarylborates appear to be an ideal arylation reagent in organic synthesis provided that all the four aryl groups could be effectively utilized. However, it has been still rather undeveloped to use tetraarylborates as aryl source in transition metal catalyzed arylation processes except for the highly reactive electrophiles [11], such as aryl iodides, acyl chlorides or more recently, allylic derivatives [15]. To our delight, under the optimal reaction conditions, the cross-coupling of sodium tetraphenylborate 4a with amide 1c could proceed smoothly to give 3cb in 64% yield.…”

“…diarylborinic acids, triarylboranes, and tetraarylborates, not only have higher atom economies as aryl reagents but also could be more economically prepared from aryl halides and trialkylborates if not hampered by sensitive functional groups [10]. However, high-order arylborons have appeared to be less reactive in transition metal catalyzed cross-couplings [11], which could be attributed to their higher reducing abilities, thus poor compatibility with highoxidation state transition metal species in catalytic cycle. We have shown that diarylborinic acids could efficiently participate in cross-couplings under proper conditions [10c,12].…”

Computer simulation of conformational transformations of 1,3-dioxanes and their 2-sila and 2-bora analogs

“…In particular, substituted 1,3,2-dioxaborinanes are used as borylating and hydroborating agents [27,79], in crosscoupling and transmetalation reactions [80], and in the preparation of 1,3-amino alcohols [8], 1,3-dioxanes [27,81], liquid crystal compositions [82], heat-resistant polymeric materials [83], and dyes [84].…”