Liu Yang-Zi, Wang Zhongao, Huang Zesheng, Yang Wu-Lin, Deng Wei-Ping
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Shanghai Key Laboratory of New Drug Design & School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China.
Org Lett. 2021 Feb 5;23(3):948-952. doi: 10.1021/acs.orglett.0c04146. Epub 2021 Jan 22.
The palladium-catalyzed asymmetric [4 + 3] cycloaddition of a sulfonyl-trimethylenemethane (TMM) donor with azadienes furnished various sulfonyl-fused azepines with exclusive regioselectivities and excellent stereoselectivities (up to >20:1 dr, >99% ee) in high yields (up to 93%). Moreover, sulfone, serving as a transient activating group of the TMM species, can be easily removed from the cycloadducts to provide the structurally simple fused azepines with excellent enantioselectivities. This strategy demonstrates sulfonyl-TMM as an effective surrogate of naked TMM with high reactivity, exclusive regioselectivity, and excellent stereoselectivity.
钯催化的磺酰基-三亚甲基甲烷（TMM）供体与氮杂二烯的不对称[4 + 3]环加成反应，以高产率（高达93%）提供了各种具有独特区域选择性和优异立体选择性（高达>20:1的非对映体比例，>99%的对映体过量）的磺酰基稠合氮杂环庚烷。此外，作为TMM物种的瞬态活化基团的砜，可以很容易地从环加成产物中除去，以提供具有优异对映选择性的结构简单的稠合氮杂环庚烷。该策略证明磺酰基-TMM是裸露TMM的有效替代物，具有高反应性、独特的区域选择性和优异的立体选择性。
