Stereoelectronic Effect for the Selectivity in C−H Insertion of Alkylidene Carbenes and Its Application to the Synthesis of Platensimycin

• Published in: Journal of the American Chemical Society Vol. 131; no. 24; pp. 8413 - 8415
• Main Authors: Yun, Sang Young, Zheng, Jun-Cheng, Lee, Daesung
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 24.06.2009; Amer Chemical Soc
• Subjects: Adamantane - chemical synthesis; Alkenes - chemistry; Aminobenzoates - chemical synthesis; Anilides - chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Ethers - chemistry; Ketones - chemistry; Methane - analogs & derivatives; Methane - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; (+/-)-PLATENSIMYCIN; PICROTOXININ; ORGANIC-SYNTHESIS; (-)-PLATENCIN; ACTIVATION; STEREOCHEMISTRY; ENANTIOSELECTIVE ROUTE; PLATENCIN; FORMAL TOTAL-SYNTHESIS; ALPHA
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja903526g

A systematic study of C−H insertion reactions with variously substituted and conformationally constrained substrates was carried out. High selectivity in the insertion between two competing C−H bonds caused by a strong stereoelectronic effect of an oxygen substituent was achieved. This regioselective C−H insertion reaction was employed as a platform to develop a concise asymmetric synthesis of platensimycin.