SmI2-Mediated Radical Cross-Couplings of alpha-Hydroxylated Aza-hemiacetals and N,S-Acetals with alpha,beta-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A(2), (-)-Uniflorine A, and (+)-7-epi-Casuarine

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	SmI2-Mediated Radical Cross-Couplings of alpha-Hydroxylated Aza-hemiacetals and N,S-Acetals with alpha,beta-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A(2), (-)-Uniflorine A, and (+)-7-epi-Casuarine
	Liu, Xue-Kui ; Qiu, Shi ; Xiang, Yong-Gang ; Ruan, Yuan-Ping ; Zheng, Xiao ; Huang, Pei-Qang ; Huang PQ(黄培强)
刊名	http://dx.doi.org/10.1021/jo200600n
	2011-06-17
关键词	N-ACYLIMINIUM IONS TERT-BUTANESULFINYL IMINES INTERMOLECULAR ADDITION-REACTIONS SAMARIUM DIIODIDE GAMMA-BUTYROLACTONES HYACINTHACINE A(2) CARBONYL-COMPOUNDS POLYHYDROXYLATED PYRROLIZIDINES DIASTEREOSELECTIVE SYNTHESIS ENANTIOSPECIFIC SYNTHESIS
英文摘要	NSF of China [20402012, 20832005]; National Basic Research Program (973 Program) of China [2010CB833200]; Natural Science Foundation of Fujian Province of China [2010J01050]; The SmI2-mediated radical coupling reactions of beta-hydroxylated pyrrolidine/piperidine aza-hemiacetals 8 and 9 and N,S-acetals 6 and 33 with alpha/beta-unsaturated compounds are described. This method allows a rapid access to beta-hydroxylated pyrrolidines, piperidines, pyrrolizidinones, and indolizidinones. Starting from N,S-acetal 33 and via a common intermediate 27, the alkaloids hyacinthacine A(2) (2), uniflorine A (3, 6-epi-casuarine), and the unnatural epimer 7-epi-casuarine (37) have been synthesized in four and five steps with overall yields of 34%, 16%, and 13%, respectively. The radical mechanism of the coupling reactions has been confirmed by controlled experiments, which also allowed deducing the anionic mechanism in the coupling between N,S-acetal 6 and carbonyl compounds. This demonstrates that the mechanisms of these SmI2-mediated reactions are switchable from Barbier-type anionic to radical by cooperative action of BF3 center dot OEt2 and t-BuOH.
语种	英语
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/64401]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Liu, Xue-Kui,Qiu, Shi,Xiang, Yong-Gang,et al. SmI2-Mediated Radical Cross-Couplings of alpha-Hydroxylated Aza-hemiacetals and N,S-Acetals with alpha,beta-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A(2), (-)-Uniflorine A, and (+)-7-epi-Casuarine[J]. http://dx.doi.org/10.1021/jo200600n,2011.
APA	Liu, Xue-Kui.,Qiu, Shi.,Xiang, Yong-Gang.,Ruan, Yuan-Ping.,Zheng, Xiao.,...&黄培强.(2011).SmI2-Mediated Radical Cross-Couplings of alpha-Hydroxylated Aza-hemiacetals and N,S-Acetals with alpha,beta-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A(2), (-)-Uniflorine A, and (+)-7-epi-Casuarine.http://dx.doi.org/10.1021/jo200600n.
MLA	Liu, Xue-Kui,et al."SmI2-Mediated Radical Cross-Couplings of alpha-Hydroxylated Aza-hemiacetals and N,S-Acetals with alpha,beta-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A(2), (-)-Uniflorine A, and (+)-7-epi-Casuarine".http://dx.doi.org/10.1021/jo200600n (2011).