Stereodivergent Synthesis of N-Heterocycles by Catalyst-Controlled, Activity-Directed Tandem Annulation of Diazo Compounds with Amino Alkynes.
A stereodivergent synthesis of five-membered N-heterocycles, such as 2,3-dihydropyrroles, and 2-methylene and 3-methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper-catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium-catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia-ene cyclization.
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China).
Kai
K
Liu
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China).
Chenghao
C
Zhu
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China).
Junxiang
J
Min
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China).
Shiyong
S
Peng
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China).
Guangyang
G
Xu
School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou 213164 (China). jtsun08@gmail.com.
Jiangtao
J
Sun
D000480:Alkynes / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000480:Alkynes; D001391:Azo Compounds; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D003300:Copper
copper; cyclizations; diazo compounds; homogeneous catalysis; rhodium