Mechanistic consideration of asymmetric CN and CC bond formations with bifunctional chiral ir and ru catalysts

Yasuharu Hasegawa, Ilya D. Gridnev, Takao Ikariya

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

The mechanism of two enantioselective reactions, direct amination of α-cyanoacetates 3 with azodicarboxylates 4 and CC bond formation reaction of α-cyanoacetates with acetylenic esters 6, catalyzed by chiral bifunctional Ir and Ru complexes, Cp*Ir[(S,S)-N-sulfonated dpen] 1 and Ru[(S,S)-N-sulfonated dpen](n 6-arene) 2 (DPEN: 1,2- diphenylethylenediamine) was studied by NMR spectroscopic analysis combined with DFT analysis. Notably, these two reactions using the same chiral amide catalysts 1, 2 and pronucleophile, α-cyanoacetates 3 gave quantitatively the conjugate adducts bearing quaternary chiral carbon centers in excellent enantiomeric excess albeit with the opposite absolute configuration depending on the acceptor molecules 4 and 6. NMR investigation of the reactions between Ir complexes 1a1c with α-cyanoacetates 3 showed that a stereoselective deprotonation reaction takes place to give an equilibrium mixture of N-bound amine complexes 8 and 9, the former with intramolecular hydrogen bonding and the latter without it, respectively. Computational study revealed the full details of the mechanism of the asymmetric CN and CC bond forming reactions catalyzed by the chiral Ir catalyst 1b. In the CN bond forming reaction, the dimethyl azodicarboxylate 4a undergoes productive bifunctional activation by a non-hydrogen-bonded N-bound complex 9b(re) resulting in the formation of the R-product through the energetically favorable transition state. On the other hand, the linear geometry of the acetylenic ester molecule 6 allows its bifunctional activation with both types of the N-bound complexes: 8b and 9b with and without the intramolecular hydrogen bond respectively. The hydrogen-bond stabilized transition state for the CC bond formation leading to the S-enantiomer is significantly lower in energy than the corresponding non-hydrogenbonded transition state leading to the R-enantiomer. Thus, chiral induction of these two reactions is determined by the structures of the acceptor molecules.

Original languageEnglish
Pages (from-to)316-334
Number of pages19
JournalBulletin of the Chemical Society of Japan
Volume85
Issue number3
DOIs
Publication statusPublished - 2012
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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