Copper‐Catalyzed Hydrosilylation with a Bowl‐Shaped Phosphane Ligand: Preferential Reduction of a Bulky Ketone in the Presence of an Aldehyde

Abstract

Hollywood bowl: A highly active copper catalyst with a bowl‐shaped phosphane (bsp) ligand was used in the hydrosilylation reaction of bulky ketones. The preferential reduction of a bulky ketone in the presence of an unprotected aldehyde is unprecedented.

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

“…At the outset of our work, however,j ust af ew terphenyl phosphine ligands, and ac onsequently small number of their complexesw ith late transition metals, had been described. [23][24][25] Our first reports centred on Rh, Ir,P ta nd Au complexes of PMe 2 Ar' phosphines (Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-R 2 ) 2 forR = Me and iPr,i ns horthand notation PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 ,r espectively), and evinced their aptitude to stabilize low-coordinate structures, as well as their potentialt oadopt different coordination modes (Figure 1), where P-bondingi sc omplement-ed by relativelyw eak M···C arene interactions with af lanking aryl ring of the terphenyl substituent. [23][24][25][26][27][28] The objective of the present work was the description of a series of PR 2 Ar' molecules selected in accordance with the following criteria.…”

“…[23][24][25] Our first reports centred on Rh, Ir,P ta nd Au complexes of PMe 2 Ar' phosphines (Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-R 2 ) 2 forR = Me and iPr,i ns horthand notation PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 ,r espectively), and evinced their aptitude to stabilize low-coordinate structures, as well as their potentialt oadopt different coordination modes (Figure 1), where P-bondingi sc omplement-ed by relativelyw eak M···C arene interactions with af lanking aryl ring of the terphenyl substituent. [23][24][25][26][27][28] The objective of the present work was the description of a series of PR 2 Ar' molecules selected in accordance with the following criteria. Firstly,b esides someP Me 2 -containing phosphines, [28,29] we set out to prepare PR 2 Ar' phosphines of the branched andc yclic alkyl groups iPr and c-C 6 H 11, respectively, which are phosphine substituents extensively employed in organometallic chemistry and catalysis.…”

“…Differentc oordination modes found for terphenyl phosphines. [23][24][25][26][27][28] analogous phosphine dicarbonyl Ni 0 compounds are unknown. Furthermore, we were surprised to learn that nearly fifty years after the generation by To lman of Ni(CO) 3 (PR 3 )c omplexes in CH 2 Cl 2 solutions, [35] there is an astonishing dearth of crystallographic information on compounds of this type.…”

Dearomative Allylation of Naphthyl Cyanohydrins by Palladium Catalysis: Catalyst-Enhanced Site Selectivity

“…meta -Disubstituted triarylphosphines likely enforce the generation of coordinatively unsaturated palladium B by steric repulsion. According to Tsuji’s work, meta -disubstituted triarylphosphines have a bowl-shaped structure, accelerating the dissociation of other ligands but providing reaction space around the metal center . In line with these reports, the use of meta -disubstituted triarylphosphines would support the generation of a coordinatively unsaturated palladium species in this catalytic system.…”

Highly Stereoselective Synthesis of 1,2-Disubstituted Indanes by Pd-Catalyzed Heck/Suzuki Sequence of Diarylmethyl Carbonates

“…The newly developed protocol can provide an avenue to chiral carbocyclic frameworks with multiple substituents, which are prevalent in natural products and bioactive molecules. Detailed investigations of the origin of uniquely high chemo- and stereoselectivity associated with DTBMP ligand and further developments of related stereospecific and stereoselective palladium catalysis are now in progress.…”