Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes - PubMed (original) (raw)

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Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Benjamin D Bergstrom et al. Angew Chem Int Ed Engl. 2021.

Abstract

Donor/donor carbenes are relatively new in the field of carbene chemistry; although applications in C-H and X-H insertion reactions are few in number, they demonstrate exquisite chemo- and stereo-selectivity. Recent reports have shown that C-H, N-H, B-H, O-H, S-H, Si-H, Ge-H, Sn-H and P-H insertion reactions are feasible with a variety of transition metal catalysts, both inter- and intramolecularly. Furthermore, high degrees of diastereo- and enantioselectivity have been observed in several cases. Methods typically involve the formation of a diazo-based carbene precursor, but procedures using diazo-free metal carbenes have been developed with significant success. This Minireview covers transition-metal catalyzed insertion reactions with donor/donor and donor carbenes, providing context for future developments in this emerging field.

Keywords: C−H insertion; X−H insertion; carbenes; catalysis; donor/donor carbenes.

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Figures

Figure 1.

Figure 1.

Reactivity of metal carbenes

Figure 2.

Figure 2.

Publication heat map of metals and insertion atoms used in insertion reactions with donor/donor carbenes

Figure 3.

Figure 3.

Common methods for diazo formation

Figure 4.

Figure 4.

Potential byproducts with carbene precursors and intermediates

Figure 5.

Figure 5.

Catalysts used in donor/donor carbene insertion reactions

Figure 6.

Figure 6.

C–H insertion reaction mechanism

Figure 7.

Figure 7.

N–H and P–H insertion reaction mechanism

Figure 8.

Figure 8.

O–H and B–H insertion reaction mechanism

Figure 9.

Figure 9.

Palladium catalyzed Si–H insertion reaction mechanism

Figure 10.

Figure 10.

C–H insertion reactions with rhodium carbenes to form indanes

Figure 11.

Figure 11.

Ruthenium catalyzed C–H insertion reactions with alkyl carbenes

Figure 12.

Figure 12.

A, Azole Csp2–H insertion reactions. B, Csp3–H insertion reactions.

Figure 13.

Figure 13.

B–H insertion reaction scope

Figure 14.

Figure 14.

Donor/Donor Sn–H insertion and potential mechanis

Figure 15.

Figure 15.

Si–H insertion reactions with alkyl/silyl carbenes

Figure 16.

Figure 16.

Donor-substituted metal carbene formation from diazo-free substrates

Figure 17.

Figure 17.

Diazo-free N–H, O–H, and Si–H insertion reactions with enynone-derived donor carbenes

Figure 18.

Figure 18.

Retro-Büchner ring expansion derived donor carbene insertion reactions

Figure 19.

Figure 19.

Cyclopropene derived donor carbene insertion reactions

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