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Iridium‐Catalyzed Dynamic Kinetic Stereoselective Allylic Etherification of Achmatowicz Rearrangement Products
Author(s) -
Zhu Zhongpeng,
Wang HaoYuan,
Simmons Christopher,
Tseng PoSen,
Qiu Xiang,
Zhang Yu,
Duan Xiyan,
Yang JingKui,
Tang Weiping
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201700950
Subject(s) - chemistry , isomerization , steric effects , allylic rearrangement , nucleophile , ligand (biochemistry) , catalysis , stereoselectivity , iridium , alcohol , medicinal chemistry , combinatorial chemistry , stereochemistry , organic chemistry , biochemistry , receptor
We recently developed a novel Ir‐catalyzed dynamic kinetic isomerization reaction for Achmatowicz rearrangement products. In this update, we show that products derived from the Achmatowicz rearrangement can also undergo Ir‐catalyzed dynamic kinetic allylic etherification in the presence of an appropriate ligand and additive to afford useful intermediates for the synthesis of carbohydrates. The addition of the triphenyl phosphite ligand shuts down the isomerization pathway and promotes the allylic etherification pathway. The addition of diphenyl phosphate improved the diastereoselectivity for the addition reaction. Interestingly, opposite diastereoselectivity was observed for sterically demanding alcohol nucleophiles compared to less sterically demanding alcohol nucleophiles. The method was also applied to the synthesis of several 2,3‐dideoxypyranosides.