TY - JOUR
T1 - Selective Ring-Opening of N-Alkyl Pyrrolidines with Chloroformates to 4-Chlorobutyl Carbamates
AU - Yu, Chunghyeon
AU - Shoaib, Mahbubul Alam
AU - Iqbal, Naeem
AU - Kim, Jun Soo
AU - Ha, Hyun Joon
AU - Cho, Eun Jin
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/7/7
Y1 - 2017/7/7
N2 - Our study shows that among aza-heterocycles of various ring sizes, including aziridines, azetidines, pyrrolidines, and piperidines, only N-alkyl pyrrolidines undergo competitive reaction pathways with chloroformates to yield N-dealkylated pyrrolidines and 4-chlorobutyl carbamates. The pathway taken depends on the substituent on the nitrogen, i.e., ring-opening with methyl and ethyl substituents and dealkylation with a benzyl substituent. Computational calculations support the substituent-dependent product formation by showing the energy difference between the transition states of both reaction pathways. Selective ring-opening reactions of N-methyl and N-ethyl pyrrolidine derivatives with chloroformates were utilized to prepare various 4-chlorobutyl carbamate derivatives as valuable 1,4-bifunctional compounds.
AB - Our study shows that among aza-heterocycles of various ring sizes, including aziridines, azetidines, pyrrolidines, and piperidines, only N-alkyl pyrrolidines undergo competitive reaction pathways with chloroformates to yield N-dealkylated pyrrolidines and 4-chlorobutyl carbamates. The pathway taken depends on the substituent on the nitrogen, i.e., ring-opening with methyl and ethyl substituents and dealkylation with a benzyl substituent. Computational calculations support the substituent-dependent product formation by showing the energy difference between the transition states of both reaction pathways. Selective ring-opening reactions of N-methyl and N-ethyl pyrrolidine derivatives with chloroformates were utilized to prepare various 4-chlorobutyl carbamate derivatives as valuable 1,4-bifunctional compounds.
UR - http://www.scopus.com/inward/record.url?scp=85022185157&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.7b00681
DO - 10.1021/acs.joc.7b00681
M3 - Article
C2 - 28593764
AN - SCOPUS:85022185157
SN - 0022-3263
VL - 82
SP - 6615
EP - 6620
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 13
ER -