Asymmetric Vinylogous Aldol-type Reactions of Aldehydes with Allyl Phosphonate and Sulfone

Asymmetric Vinylogous Aldol-type Reactions of Aldehydes with Allyl Phosphonate and Sulfone
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醛与膦酸烯丙酯和砜的不对称乙烯醇醛型反应

DOI:
10.1016/j.isci.2019.03.010
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发表时间:
2019-03
期刊:
影响因子:
5.8
通讯作者:
Yin Liang
Yin Liang
中科院分区:
综合性期刊2区
文献类型:
--
作者:
Yue Wen-Jun;Zhang Cheng-Yuan;Yin Liang

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首次发现了两种醛与膦酸烯丙基和砜的催化不对称乙烯醛型反应,收率较高。大体积配体- (R)- dtbm - segphos被发现是完美控制区域和对映体选择性的关键。利用膦酸盐和砜基团,成功地实现了葡萄产物(包括霍纳-沃兹沃思-埃蒙斯和朱莉娅烯烃)的转化。该方法已成功地应用于天然产物的不对称合成。
Two catalytic asymmetric vinylogous aldol-type reactions of aldehydes with allyl phosphonate and allyl sulfone have been uncovered in good to high yields for the first time. The bulky ligand—(R)-DTBM-SEGPHOS—was found to be the key to perfectly control both regio- and enantioselectivities. Transformations of the vinylogous products (including Horner-Wadsworth-Emmons and Julia olefinations) were successfully realized by virtue of the phosphonate and sulfone moieties. Moreover, the present methodology was successfully applied in the asymmetric synthesis of natural products.
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