Triple C–H activation of 1,5-bis(di-tert-butylphosphino)-2-(S)-dimethylaminopentane on ruthenium gives a chiral carbene complex

Abstract

This communication reports the preparation of a novel trans-chelating diphosphine, 1,5-bis(di-tert-butylphosphino)-2-(S)-dimethylaminopentane, that undergoes triple C-H activation in reaction with [RuCl2(p-cymene)]2 to give a chiral square-pyramidal 16-electron carbene complex of ruthenium.

Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

“…The fast and selective formation of the cationic complex (9) of the meso isomer 5 RSR allowed for the separation of the 5 RRR and 5 SSR isomers of the bisphosphane 5. Most common synthetic approaches to P-chirogenic bisphosphanes involve the introduction of chiral spacers between the two phosphorus atoms, [11][12][13][14][15][16] synthesis from chiral borane-protected monophosphanes, [17][18] as well as procedures employing the enantiodifferentiated deprotonation of prochiral phosphane-boranes in the presence of chiral inductors. As a result, the stereoconversion is accompanied by a change in not only the value but also in the sign of the specific rotation, [α] D 20 .…”

Phosphines and Related Tervalent Phosphorus Systems

“…415 Bis(phosphinomethyl)amino systems have also been described, e.g., (166), 416 the amphiphilic and water-soluble systems (167), 417 and a bis(aminomethylphosphine) derived from 3,4-diaminotoluene. 418 The related reactions of bis(hydroxymethyl)organophosphines with primary amines have led to the isolation of new cyclic-and macrocyclic-aminomethylphosphines, e.g., (168). 419,420 A new macrocyclic tetraphosphine has also been isolated from the reaction of a disecondary bis(phosphino)propane with formaldehyde and benzylamine.…”

“…165,166 Chiral C 2 -symmetric 1,4-dioxanyldiphosphines, e.g., (84), have been prepared from tartrate esters. 167 Routes to a number of P,P,N-donor systems have been developed, including a trans-chelating 1,5-bis(di-t-butylphosphino)-2-(S)-dimethylaminopentane, 168 2,2 0 -bis(diphenylphosphino)diphenylamine, 169 and a series of tripod ligands (85) involving phosphine and dialkylamine or N-pyrazolyl donors. 170,171 A phosphide route has also been used to prepare 2-(diphenylphosphinoethyl)-3,5-dimethylpyrazole.…”

The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 2002

“…636) through triple C-H activation of amine-containing diphosphines (e.g. 635) was also noted [572]. Analogous ruthenium and osmium carbene complexes (e.g.…”