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Alkyne Carbonylation by Radicals: Tin‐Radical‐Catalyzed Synthesis of α‐Methylene Amides from 1‐Alkynes, Carbon Monoxide, and Amines

2005; Wiley; Volume: 44; Issue: 7 Linguagem: Inglês

10.1002/anie.200461954

1521-3773

Yoshitaka Uenoyama, Takahide Fukuyama, Osamu Nobuta, Hiroshi Matsubara, Ilhyong Ryu,

Catalytic C–H Functionalization Methods

Angewandte Chemie International EditionVolume 44, Issue 7 p. 1075-1078 Communication Alkyne Carbonylation by Radicals: Tin-Radical-Catalyzed Synthesis of α-Methylene Amides from 1-Alkynes, Carbon Monoxide, and Amines† Yoshitaka Uenoyama, Yoshitaka Uenoyama Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorTakahide Fukuyama Dr., Takahide Fukuyama Dr. Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorOsamu Nobuta, Osamu Nobuta Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorHiroshi Matsubara Dr., Hiroshi Matsubara Dr. Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorIlhyong Ryu Prof., Ilhyong Ryu Prof. [email protected] Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this author Yoshitaka Uenoyama, Yoshitaka Uenoyama Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorTakahide Fukuyama Dr., Takahide Fukuyama Dr. Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorOsamu Nobuta, Osamu Nobuta Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorHiroshi Matsubara Dr., Hiroshi Matsubara Dr. Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this authorIlhyong Ryu Prof., Ilhyong Ryu Prof. [email protected] Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: (+81) 72-254-9695Search for more papers by this author First published: 21 January 2005 https://doi.org/10.1002/anie.200461954Citations: 128 † This work was supported by Grant-in-Aid for Scientific Research (B) from JSPS. Technical support of Library & Science Information Center, Osaka Prefecture University for the computational study is gratefully acknowledged. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract A convergent synthesis of α-methylene amides exploits a hybrid radical/ionic concept in which radical carbonylation of alkynes is followed by ionic trapping of the resulting carbonyl-containing radical species with amines (see scheme). The reaction of substituted terminal alkynes with pressurized CO, Bu3SnH, and 2,2′-azobisisobutyronitrile in the presence of a large excess of amines gave good yields of the corresponding α-methylene amides. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z461954_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1For reviews on radical chemistry, see 1a Radicals in Organic Synthesis, Vols. 1 and 2 (Eds.: ), Wiley-VCH, Weinheim, 2001; 1bD. P. Curran, N. A. Porter, B. Giese, Stereochemistry of Radical Reactions, VCH, Weinheim, 1996; 1cW. B. Motherwell, D. 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