Fundamental Aspects of the Metal-Catalyzed C–H Bond Functionalization by Diazocarbenes: Guiding Principles for Design of Catalyst with Non-redox-Active Metal (Such as Ca) and Non-Innocent Ligand
Adrian Varela-Alvarez
Emory University, Cherry L. Emerson Center for Scientific Computation, 1515 Dickey Drive, Atlanta, Georgia 30322, USA
Search for more papers by this authorDjamaladdin G. Musaev
Emory University, Cherry L. Emerson Center for Scientific Computation, 1515 Dickey Drive, Atlanta, Georgia 30322, USA
Search for more papers by this authorAdrian Varela-Alvarez
Emory University, Cherry L. Emerson Center for Scientific Computation, 1515 Dickey Drive, Atlanta, Georgia 30322, USA
Search for more papers by this authorDjamaladdin G. Musaev
Emory University, Cherry L. Emerson Center for Scientific Computation, 1515 Dickey Drive, Atlanta, Georgia 30322, USA
Search for more papers by this authorValentine P. Ananikov
Russian Academy of Sciences, Zelinsky, Institute of Organic Chemistry, 47 Leninski Prospect, 119991 Moscow, Russia
Search for more papers by this authorSummary
We analyzed electronic factors affecting the mechanism of metal-catalyzed C–H bond alkylation by diazocarbene precursors. The analyses showed that e efficient metal-catalyzed alkylation of C–H bond by diazocarbenes requires a fine balance (i) of the triplet and singlet electronic states of carbenes: availability of singlet and triplet states is crucial for electrophilic and nucleophilic character of carbene fragment of metallocarbenes; and (ii) in the metal–carbene bond strength: a strong metal–carbene bond is required for facile diazocarbene decomposition, while weak metal–carbene interaction is beneficiary for the metallo-carbene reaction with various substrates. The aforementioned delicate balance is predicted to be achieved by utilizing a combination of (i) transition metals with smaller energy gap between their s1dn−1 and s0dn electron configurations, and triplet carbenes with an energetically close singlet electronic state or/and (ii) transition metals with a ground s0dn electron configuration and carbenes with a singlet ground electronic state.
Bearing in mind these analyses and our previous studies in the field, we proposed a conceptually new approach based on the use of an earth-abundant transition-metal complex containing a non-redox-active metal center and redox-active (non-innocent) ligand as a catalyst. We demonstrated our prediction using [(PDI)Ca(THF)3], where PDI is a non-innocent pyridine-2,6-diimine ligand, to catalyze the benzylic (of MeCH2Ph substrate) C–H bond alkylation by unsubstituted and diphenyl (known as donor-donor)-substituted diazocarbene precursors, N2CH2 and N2CPh2. It was shown that the [(PDI)Ca(THF)3], 4, complex containing the non-redox Ca(II)-center and a non-innocent PDI ligand promotes the C–H bond alkylation of MeCH2Ph by unsubstituted N2CH2 diazocarbene. Reaction of 4 with N2CH2 is found to proceed with a barrier of about 17.6 kcal mol−1 and is only slightly (2.8 kcal mol−1) exergonic. During this reaction, only one electron is transferred from the PDI ligand to the carbene fragment of the metallocarbene intermediate 8. Thus, the resultant [(PDI)Ca(THF)2]-carbene intermediate is diradical with one unpaired electron each on the PDI and carbene ligands. This intermediate reacts with benzylic C–H bond via the H-atom abstraction mechanism of a 20.3 kcal mol−1 energy barrier. We predicted and demonstrated that inclusion of donor substituents to the carbene fragment, that is, using N2CPh2 as a substituent diazo precursor in place of N2CH2, makes the diazocarbene decomposition more exergonic (about 17.8 kcal mol−1) and the [(PDI)Ca(THF)3]-catalyzed benzylic (of the MeCH2Ph substrate) C–H bond alkylation more practical.
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