N-Heterocyclic Olefin Catalysis for the Ring Opening of Cyclic Amidine Compounds: A Pathway to the Synthesis of ϵ-Caprolactam- and γ-Lactam-Derived Amines

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Abstract

For the first time, 1,2-dimethyl-3-ethylimidazolium iodide (1a) catalyzes the ring opening of the bicyclic amidine system of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene) on reaction with aldehydes. The mechanism here proposed involves an N-heterocyclic olefin (NHO) catalytic species that acts as a nucleophile to promote the cyclic amidine ring opening. The resulting ϵ-caprolactam- and γ-lactam-derived imines were obtained in moderate to excellent yields (28-99%) and reduced to the corresponding amines by sodium borohydride. Confirmation of the imine product was achieved via single-crystal X-ray diffraction studies.

Original languageEnglish
Pages (from-to)3793-3800
Number of pages8
JournalJournal of Organic Chemistry
Volume84
Issue number7
DOIs
Publication statusPublished - 5 Apr 2019

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Caprolactam
Amidines
Lactams
Imines
Alkenes
Catalysis
Amines
Nucleophiles
Iodides
Aldehydes
Single crystals
X ray diffraction

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@article{cc9e6e11d5d046bdab001ebf97c1e1cd,
title = "N-Heterocyclic Olefin Catalysis for the Ring Opening of Cyclic Amidine Compounds: A Pathway to the Synthesis of ϵ-Caprolactam- and γ-Lactam-Derived Amines",
abstract = "For the first time, 1,2-dimethyl-3-ethylimidazolium iodide (1a) catalyzes the ring opening of the bicyclic amidine system of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene) on reaction with aldehydes. The mechanism here proposed involves an N-heterocyclic olefin (NHO) catalytic species that acts as a nucleophile to promote the cyclic amidine ring opening. The resulting ϵ-caprolactam- and γ-lactam-derived imines were obtained in moderate to excellent yields (28-99{\%}) and reduced to the corresponding amines by sodium borohydride. Confirmation of the imine product was achieved via single-crystal X-ray diffraction studies.",
author = "Daniela Peixoto and Gabriela Malta and Hugo Cruz and S{\'o}nia Barroso and Carvalho, {Ana Lu{\'i}sa} and Ferreira, {Lu{\'i}sa M.} and Branco, {Paula S.}",
note = "info:eu-repo/grantAgreement/FCT/3599-PPCDT/127013/PT# UID/QUI/50006/2019). UID/Multi/04378/2019. POCI-01-0145-FEDER-007728. RECUBBB-BEP/0124/2012. Sem PDF conforme despacho.",
year = "2019",
month = "4",
day = "5",
doi = "10.1021/acs.joc.8b02823",
language = "English",
volume = "84",
pages = "3793--3800",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "AMER CHEMICAL SOC",
number = "7",

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TY - JOUR

T1 - N-Heterocyclic Olefin Catalysis for the Ring Opening of Cyclic Amidine Compounds: A Pathway to the Synthesis of ϵ-Caprolactam- and γ-Lactam-Derived Amines

AU - Peixoto, Daniela

AU - Malta, Gabriela

AU - Cruz, Hugo

AU - Barroso, Sónia

AU - Carvalho, Ana Luísa

AU - Ferreira, Luísa M.

AU - Branco, Paula S.

N1 - info:eu-repo/grantAgreement/FCT/3599-PPCDT/127013/PT# UID/QUI/50006/2019). UID/Multi/04378/2019. POCI-01-0145-FEDER-007728. RECUBBB-BEP/0124/2012. Sem PDF conforme despacho.

PY - 2019/4/5

Y1 - 2019/4/5

N2 - For the first time, 1,2-dimethyl-3-ethylimidazolium iodide (1a) catalyzes the ring opening of the bicyclic amidine system of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene) on reaction with aldehydes. The mechanism here proposed involves an N-heterocyclic olefin (NHO) catalytic species that acts as a nucleophile to promote the cyclic amidine ring opening. The resulting ϵ-caprolactam- and γ-lactam-derived imines were obtained in moderate to excellent yields (28-99%) and reduced to the corresponding amines by sodium borohydride. Confirmation of the imine product was achieved via single-crystal X-ray diffraction studies.

AB - For the first time, 1,2-dimethyl-3-ethylimidazolium iodide (1a) catalyzes the ring opening of the bicyclic amidine system of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene) on reaction with aldehydes. The mechanism here proposed involves an N-heterocyclic olefin (NHO) catalytic species that acts as a nucleophile to promote the cyclic amidine ring opening. The resulting ϵ-caprolactam- and γ-lactam-derived imines were obtained in moderate to excellent yields (28-99%) and reduced to the corresponding amines by sodium borohydride. Confirmation of the imine product was achieved via single-crystal X-ray diffraction studies.

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U2 - 10.1021/acs.joc.8b02823

DO - 10.1021/acs.joc.8b02823

M3 - Article

VL - 84

SP - 3793

EP - 3800

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 7

ER -