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.

Diastereoselective Lewis acid-mediated additions of nucleophilica lkenest oN-sulfonyli mines are reported. The canonical polar Felkin-Anhm odel describing additions to carbonyls does not adequately describe analogousa dditions to N-sulfonyl imines.H erein, we describe the develop-ment of conditions to produce both syn and anti products with high diastereoselectivity and good yields. As tereoelectronicm odel consistent with experimental outcomesi sa lso proposed.[a] L.

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.

We employ a single catalyst/oxidant system to enable the asymmetric syntheses of indolines, benzodihydrothiophenes, and indanes by C-H insertion of donor/donor carbenes. This methodology enables the rapid construction of densely substituted five-membered rings that form the core of many drug targets and natural products. Furthermore, oxidation of hydrazones to the corresponding diazo compounds proceeds in situ, enabling a relatively facile one- or two-pot protocol in which isolation of potentially explosive diazo alkanes is avoided. Regioselectivity studies were performed to determine the impact of sterics and electronics in donor/donor metal carbene C-H insertions to form indolines. This methodology was applied to a variety of substrates in high yield, diastereomeric, and enantiomeric ratios and to the synthesis of a patented indane estrogen receptor agonist with anti-cancer activity.

We employasingle catalyst/oxidant system to enable the asymmetric syntheses of indolines,b enzodihydrothiophenes,a nd indanes by CÀHi nsertion of donor/donor carbenes.T his methodology enables the rapid construction of densely substituted five-membered rings that form the core of many drug targets and natural products.F urthermore,o xidation of hydrazones to the corresponding diazoc ompounds proceeds in situ, enabling ar elatively facile one-or two-pot protocol in which isolation of potentially explosive diazo alkanes is avoided. Regioselectivity studies were performed to determine the impact of sterics and electronics in donor/donor metal carbene C À Hinsertions to form indolines.This methodology was applied to av ariety of substrates in high yield, diastereomeric,and enantiomeric ratios and to the synthesis of ap atented indane estrogen receptor agonist with anti-cancer activity.