Rhodium-Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)-α-Tocopherol

被引：0

作者：

Daiger, Martin T. ^{[1
]}

Giofre, Sabrina ^{[2
]}

Berthold, Dino ^{[3
]}

Breit, Bernhard ^{[1
]}

机构：

[1] Albert Ludwigs Univ Freiburg, Inst Organ Chem, Albertstr 21, D-79104 Freiburg, Germany

[2] Univ Milan, Sez Chim Gen & Organ A Marchesini, DISFARM, Via Venezian 21, I-20133 Milan, Italy

[3] Ludwig Maximilians Univ Munchen, Dept Chem, Butenandtstr 5-13,Haus F, D-81377 Munich, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2024年 / 30卷 / 46期

关键词：

Allenes; Allylic products; Asymmetric catalysis; Rhodium; (R; R; R)-alpha-tocopherol; ASYMMETRIC ALLYLATION; TERMINAL OLEFINS; ALLYLIC ALCOHOLS; ALKYNES; STRATEGY; REGIO; ISOCHROMANS; DERIVATIVES; CYCLIZATION; TRIAZOLES;

D O I：

10.1002/chem.202402010

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report herein of a novel, enantioselective and rhodium- catalyzed cyclisation of allenyl alcohols towards chiral alpha-vinylic, cyclic ethers employing a rhodium/(R,R)-Me-ferrocelane catalyst. The corresponding chiral cyclic products were obtained in general high yields and enantioselectivities. The synthetic value of our obtained products was further exemplified by transformations of the allylic ether function. Furthermore, applying our newly developed method in our previously reported route towards the total synthesis of (R,R,R)-alpha-tocopherol, we accomplished a significantly improved 2nd generation synthesis of the chromane building providing a total number of 13 steps and an overall total yield of 27 %.

引用

页数：6

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