Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
C. Eugene Bennett Department of Chemistry, West Virginia University , Morgantown, West Virginia 26505, United States.
Org Lett. 2017 Sep 1;19(17):4636-4639. doi: 10.1021/acs.orglett.7b02261. Epub 2017 Aug 23.
A rhodium-catalyzed cycloisomerization and oxidation of tethered dienynes for the synthesis of indanes is described. An auxiliary fragmentation/olefination method (also described herein) provides novel access to tethered alkyne-dienoate substrates. The reported method circumvents current limitations in and expands the scope of inverse-demand Diels-Alder-type cycloadditions. Traditional discovery substrates involving malonate-, ether-, and sulfonamide-based tethers are problematic in the current methodology, underscoring the unique virtue of neopentylene-tethered substrates for reaction discovery.
本文描述了一种铑催化的连接二炔的环异构化和氧化反应，用于合成茚满。辅助断裂/烯烃化方法（本文也有描述）为连接的炔二羧酸酯底物提供了新的途径。所报道的方法规避了当前反需求狄尔斯-阿尔德型环加成的限制，并扩展了其范围。在当前方法中，涉及丙二酸酯、醚和磺酰胺基连接体的传统发现底物存在问题，这突显了新戊烯连接体底物在反应发现方面的独特优势。
