A Carbene-Extended ATRA Reaction.

Atom-transfer radical addition (ATRA) reactions have gained a strong foothold in organic synthesis by virtue of their operational simplicity, synthetic versatility, and perfect atom economy. A rich chemical space can be accessed through clever combinations of the simple starting materials. Many variations of this general motif have been reported. However, the vast majority involve the addition of an organic halide across a C=C double bond, resulting in the formation of 1,2-bifunctional products. This report introduces a significant expansion of this general reactivity concept to give 1,3-bifunctional adducts through the combination of 1,1-ATRA to a carbenoid and 1,2-ATRA to an alkyne. Both processes operate under mild conditions (RT, 5 h) with the same commercial catalyst (CoBr2 , dppbz).