Copper-catalyzed facile carbon-carbon bond forming reactions at the α-position of α,α,γ-trichlorinated γ-lactams

Copper Catalyzed Atom Transfer Radical Cyclization Reactions

“…The ability to sequence an ATRC reaction with another atom transfer process is a powerful technique to set‐up complex skeletal frameworks in an efficient manner. A tandem ATRC‐ATRA protocol has been developed which takes advantage of the generally faster rates of intramolecular cyclization vs. intermolecular addition 54. Heating 64a and methylene‐cyclohexane with 10 mol‐% Cu(Bpy)Cl for 1 h in DCE at reflux furnished 109 in 85 % yield as mainly the cis isomer (Scheme ).…”

“…Monocyclization of amide 114 (X = NBn) gives 115 but tandem cyclization to give 116 can also be achieved by carrying out the ATRC reaction with 30 mol‐% Cu(Bpy)Cl at room temperature or at 40 °C respectively. Elimination of the exocyclic tertiary chloride from ATRC‐ATRC product 117 occurred upon chromatography 54. The same strategy was used as the key step in the synthesis of the eunicellin class of natural products using trichloroacetatate derivatives 114 (X = O).…”

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

“…[47] A variant has been reported by the group of Nagashima, showing that the synthesis of trichlorinated -lactams can be achieved by an ATRC reaction of Nallyltrichloroacetamides in the presence of CuC1 and bipyridine at room temperature, followed by a second ATRA with 1-hexene (Scheme 12 b). [48] The double ATRC-ATRC version is also known, exemplified by the synthesis of bicyclic lactams (Scheme 12 c). [48] With the same CuCl/bipyridine system, N-tosyl-N-geranyl trichloroacetamide converted into the corresponding bicyclic lactam in a one-pot reaction.…”

“…[48] The double ATRC-ATRC version is also known, exemplified by the synthesis of bicyclic lactams (Scheme 12 c). [48] With the same CuCl/bipyridine system, N-tosyl-N-geranyl trichloroacetamide converted into the corresponding bicyclic lactam in a one-pot reaction. The monocyclic lactam can be isolated as a 2:1 mixture of diastereomers, probing that the reaction is sequential.…”

Ruthenium-catalyzed Atom Transfer Radical Addition Reactions

“…For example, functionalized lactams were obtained by AT RC-ATRC [14] or by AT RC-ATRA reaction sequences. [15] We have recently reported that it is possible to perform double Kharasch reactions with dichlorinated compounds in a purely intermolecular fashion (Scheme 3b). [16] The AT RA-ATRA reaction sequence can be carried out with two types of olefins allowing the preparation of structurally diverse 1,5-dichlorides.…”