Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles

Herein, we present a general synthetic strategy for the preparation of 3-, 4-, 5-, and 6-membered heterocyclic unnatural amino acid derivatives by exploiting facile Mannich-type reactions between readily available N-alkyl- and N-aryl-substituted diisopropyl iminomalonates and a wide range of soft an...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of organic chemistry 2019-06, Vol.84 (11), p.7066-7099
Hauptverfasser: Kattamuri, Padmanabha V, Bhakta, Urmibhusan, Siriwongsup, Surached, Kwon, Doo-Hyun, Alemany, Lawrence B, Yousufuddin, Muhammed, Ess, Daniel H, Kürti, László
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 7099
container_issue 11
container_start_page 7066
container_title Journal of organic chemistry
container_volume 84
creator Kattamuri, Padmanabha V
Bhakta, Urmibhusan
Siriwongsup, Surached
Kwon, Doo-Hyun
Alemany, Lawrence B
Yousufuddin, Muhammed
Ess, Daniel H
Kürti, László
description Herein, we present a general synthetic strategy for the preparation of 3-, 4-, 5-, and 6-membered heterocyclic unnatural amino acid derivatives by exploiting facile Mannich-type reactions between readily available N-alkyl- and N-aryl-substituted diisopropyl iminomalonates and a wide range of soft anionic C-nucleophiles without using any catalyst or additive. Fully substituted aziridines were obtained in a single step when enolates of α-bromo esters were employed as nucleophiles. Enantiomerically enriched azetidines, γ-lactones, and tetrahydroquinolines were obtained via a two-step catalytic asymmetric reduction and cyclization sequence from ketone enolate-derived adducts. Finally, highly substituted γ-lactams were prepared in one pot from adducts obtained using acetonitrile-derived carbanions. Overall, this work clearly demonstrates the utility of iminomalonates as highly versatile building blocks for the practical and scalable synthesis of structurally diverse heterocycles.
doi_str_mv 10.1021/acs.joc.9b00681
format Article
fullrecord <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7879484</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2213148709</sourcerecordid><originalsourceid>FETCH-LOGICAL-a388t-78618d9fcad813a86539098d01436e711296cdbc5327dccb2727f57fbeac9083</originalsourceid><addsrcrecordid>eNp1kTtvFDEUhS1ERJZATYdcIpHZ-DF-NUhoCSRSgGLTWx6Ph3U0Mx5sT6Tp6Kn4i_wSnOwShQIX15bu-c61fQB4hdEaI4LPjE3rm2DXqkGIS_wErDAjqOIK1U_BCiFCKko4PQbPU7pBZTHGnoFjihFSjNMV-LldxrxzyScYOrjNcbZ5jqbvF_jB37qYHKS_f_w6hfV9ZffVjC3k5fTZDY2LroUXLrsY7GJ7l2AXw1Bgn8IUw7T08HLwYxhMH0aTS_-O3oYuw02x-DIXJkw7X8gX4KgzfXIvD_sJuP54fr25qK6-frrcvL-qDJUyV0JyLFvVWdNKTI3kjCqkZItwTbkTGBPFbdtYRolorW2IIKJjomucsQpJegLe7W2nuRlca92Yy4P1FP1g4qKD8frfzuh3-lu41UIKVcu6GLw5GMTwfXYp68En6_rejC7MSROCKa6lQKpIz_ZSG0NK0XUPYzDSdwnqkqAuCepDgoV4_fh2D_q_kRXB271gT85xLH_1X7s_87ytdw</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2213148709</pqid></control><display><type>article</type><title>Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles</title><source>American Chemical Society Journals</source><creator>Kattamuri, Padmanabha V ; Bhakta, Urmibhusan ; Siriwongsup, Surached ; Kwon, Doo-Hyun ; Alemany, Lawrence B ; Yousufuddin, Muhammed ; Ess, Daniel H ; Kürti, László</creator><creatorcontrib>Kattamuri, Padmanabha V ; Bhakta, Urmibhusan ; Siriwongsup, Surached ; Kwon, Doo-Hyun ; Alemany, Lawrence B ; Yousufuddin, Muhammed ; Ess, Daniel H ; Kürti, László</creatorcontrib><description>Herein, we present a general synthetic strategy for the preparation of 3-, 4-, 5-, and 6-membered heterocyclic unnatural amino acid derivatives by exploiting facile Mannich-type reactions between readily available N-alkyl- and N-aryl-substituted diisopropyl iminomalonates and a wide range of soft anionic C-nucleophiles without using any catalyst or additive. Fully substituted aziridines were obtained in a single step when enolates of α-bromo esters were employed as nucleophiles. Enantiomerically enriched azetidines, γ-lactones, and tetrahydroquinolines were obtained via a two-step catalytic asymmetric reduction and cyclization sequence from ketone enolate-derived adducts. Finally, highly substituted γ-lactams were prepared in one pot from adducts obtained using acetonitrile-derived carbanions. Overall, this work clearly demonstrates the utility of iminomalonates as highly versatile building blocks for the practical and scalable synthesis of structurally diverse heterocycles.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/acs.joc.9b00681</identifier><identifier>PMID: 31009563</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of organic chemistry, 2019-06, Vol.84 (11), p.7066-7099</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a388t-78618d9fcad813a86539098d01436e711296cdbc5327dccb2727f57fbeac9083</citedby><cites>FETCH-LOGICAL-a388t-78618d9fcad813a86539098d01436e711296cdbc5327dccb2727f57fbeac9083</cites><orcidid>0000-0002-1176-9515 ; 0000-0001-5689-9762 ; 0000-0002-3412-5894 ; 0000-0002-5381-1347</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.joc.9b00681$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.joc.9b00681$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31009563$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kattamuri, Padmanabha V</creatorcontrib><creatorcontrib>Bhakta, Urmibhusan</creatorcontrib><creatorcontrib>Siriwongsup, Surached</creatorcontrib><creatorcontrib>Kwon, Doo-Hyun</creatorcontrib><creatorcontrib>Alemany, Lawrence B</creatorcontrib><creatorcontrib>Yousufuddin, Muhammed</creatorcontrib><creatorcontrib>Ess, Daniel H</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><title>Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Herein, we present a general synthetic strategy for the preparation of 3-, 4-, 5-, and 6-membered heterocyclic unnatural amino acid derivatives by exploiting facile Mannich-type reactions between readily available N-alkyl- and N-aryl-substituted diisopropyl iminomalonates and a wide range of soft anionic C-nucleophiles without using any catalyst or additive. Fully substituted aziridines were obtained in a single step when enolates of α-bromo esters were employed as nucleophiles. Enantiomerically enriched azetidines, γ-lactones, and tetrahydroquinolines were obtained via a two-step catalytic asymmetric reduction and cyclization sequence from ketone enolate-derived adducts. Finally, highly substituted γ-lactams were prepared in one pot from adducts obtained using acetonitrile-derived carbanions. Overall, this work clearly demonstrates the utility of iminomalonates as highly versatile building blocks for the practical and scalable synthesis of structurally diverse heterocycles.</description><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNp1kTtvFDEUhS1ERJZATYdcIpHZ-DF-NUhoCSRSgGLTWx6Ph3U0Mx5sT6Tp6Kn4i_wSnOwShQIX15bu-c61fQB4hdEaI4LPjE3rm2DXqkGIS_wErDAjqOIK1U_BCiFCKko4PQbPU7pBZTHGnoFjihFSjNMV-LldxrxzyScYOrjNcbZ5jqbvF_jB37qYHKS_f_w6hfV9ZffVjC3k5fTZDY2LroUXLrsY7GJ7l2AXw1Bgn8IUw7T08HLwYxhMH0aTS_-O3oYuw02x-DIXJkw7X8gX4KgzfXIvD_sJuP54fr25qK6-frrcvL-qDJUyV0JyLFvVWdNKTI3kjCqkZItwTbkTGBPFbdtYRolorW2IIKJjomucsQpJegLe7W2nuRlca92Yy4P1FP1g4qKD8frfzuh3-lu41UIKVcu6GLw5GMTwfXYp68En6_rejC7MSROCKa6lQKpIz_ZSG0NK0XUPYzDSdwnqkqAuCepDgoV4_fh2D_q_kRXB271gT85xLH_1X7s_87ytdw</recordid><startdate>20190607</startdate><enddate>20190607</enddate><creator>Kattamuri, Padmanabha V</creator><creator>Bhakta, Urmibhusan</creator><creator>Siriwongsup, Surached</creator><creator>Kwon, Doo-Hyun</creator><creator>Alemany, Lawrence B</creator><creator>Yousufuddin, Muhammed</creator><creator>Ess, Daniel H</creator><creator>Kürti, László</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-1176-9515</orcidid><orcidid>https://orcid.org/0000-0001-5689-9762</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid><orcidid>https://orcid.org/0000-0002-5381-1347</orcidid></search><sort><creationdate>20190607</creationdate><title>Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles</title><author>Kattamuri, Padmanabha V ; Bhakta, Urmibhusan ; Siriwongsup, Surached ; Kwon, Doo-Hyun ; Alemany, Lawrence B ; Yousufuddin, Muhammed ; Ess, Daniel H ; Kürti, László</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a388t-78618d9fcad813a86539098d01436e711296cdbc5327dccb2727f57fbeac9083</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kattamuri, Padmanabha V</creatorcontrib><creatorcontrib>Bhakta, Urmibhusan</creatorcontrib><creatorcontrib>Siriwongsup, Surached</creatorcontrib><creatorcontrib>Kwon, Doo-Hyun</creatorcontrib><creatorcontrib>Alemany, Lawrence B</creatorcontrib><creatorcontrib>Yousufuddin, Muhammed</creatorcontrib><creatorcontrib>Ess, Daniel H</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kattamuri, Padmanabha V</au><au>Bhakta, Urmibhusan</au><au>Siriwongsup, Surached</au><au>Kwon, Doo-Hyun</au><au>Alemany, Lawrence B</au><au>Yousufuddin, Muhammed</au><au>Ess, Daniel H</au><au>Kürti, László</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2019-06-07</date><risdate>2019</risdate><volume>84</volume><issue>11</issue><spage>7066</spage><epage>7099</epage><pages>7066-7099</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>Herein, we present a general synthetic strategy for the preparation of 3-, 4-, 5-, and 6-membered heterocyclic unnatural amino acid derivatives by exploiting facile Mannich-type reactions between readily available N-alkyl- and N-aryl-substituted diisopropyl iminomalonates and a wide range of soft anionic C-nucleophiles without using any catalyst or additive. Fully substituted aziridines were obtained in a single step when enolates of α-bromo esters were employed as nucleophiles. Enantiomerically enriched azetidines, γ-lactones, and tetrahydroquinolines were obtained via a two-step catalytic asymmetric reduction and cyclization sequence from ketone enolate-derived adducts. Finally, highly substituted γ-lactams were prepared in one pot from adducts obtained using acetonitrile-derived carbanions. Overall, this work clearly demonstrates the utility of iminomalonates as highly versatile building blocks for the practical and scalable synthesis of structurally diverse heterocycles.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>31009563</pmid><doi>10.1021/acs.joc.9b00681</doi><tpages>34</tpages><orcidid>https://orcid.org/0000-0002-1176-9515</orcidid><orcidid>https://orcid.org/0000-0001-5689-9762</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid><orcidid>https://orcid.org/0000-0002-5381-1347</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 0022-3263
ispartof Journal of organic chemistry, 2019-06, Vol.84 (11), p.7066-7099
issn 0022-3263
1520-6904
language eng
recordid cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_7879484
source American Chemical Society Journals
title Synthesis of Structurally Diverse 3‑, 4‑, 5‑, and 6‑Membered Heterocycles from Diisopropyl Iminomalonates and Soft C‑Nucleophiles
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-24T19%3A26%3A24IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Synthesis%20of%20Structurally%20Diverse%203%E2%80%91,%204%E2%80%91,%205%E2%80%91,%20and%206%E2%80%91Membered%20Heterocycles%20from%20Diisopropyl%20Iminomalonates%20and%20Soft%20C%E2%80%91Nucleophiles&rft.jtitle=Journal%20of%20organic%20chemistry&rft.au=Kattamuri,%20Padmanabha%20V&rft.date=2019-06-07&rft.volume=84&rft.issue=11&rft.spage=7066&rft.epage=7099&rft.pages=7066-7099&rft.issn=0022-3263&rft.eissn=1520-6904&rft_id=info:doi/10.1021/acs.joc.9b00681&rft_dat=%3Cproquest_pubme%3E2213148709%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2213148709&rft_id=info:pmid/31009563&rfr_iscdi=true