Enantioselective Synthesis of Multisubstituted Allenes by Cooperative Cu/Pd‐Catalyzed 1,4‐Arylboration of 1,3‐Enynes

A cooperative Cu/Pd‐catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl2(dppf) complexes as catalysts, the 1,4‐arylboration of 1,3‐enynes provides an efficient approach to trisubstituted chiral allenes with up to...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-01, Vol.59 (3), p.1176-1180
Main Authors: Liao, Yang, Yin, Xuemei, Wang, Xihong, Yu, Wangzhi, Fang, Dongmei, Hu, Lianrui, Wang, Min, Liao, Jian
Format: Article
Language:English
Subjects:
allenes
Catalysts
Chemical synthesis
copper
Enantiomers
enantioselectivity
palladium
Palladium chloride
Phosphine
Phosphines
Substrates
synthetic methods
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Summary:A cooperative Cu/Pd‐catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl2(dppf) complexes as catalysts, the 1,4‐arylboration of 1,3‐enynes provides an efficient approach to trisubstituted chiral allenes with up to 92 % yield and 97:3 er. Furthermore, by using 2‐substituted 1,3‐enynes as substrates, the tetrasubstituted chiral allenes were successfully generated using this strategy. Finally, theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate‐limiting step of this transformation. A cooperative Cu/Pd‐catalyzed enantioselective 1,4‐arylboration of 1,3‐enynes was developed with excellent yields and enantioselectivities, and broad substrate scope. By employing this method, tri‐ and tetrasubstituted axially chiral allenes were prepared. Theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate‐limiting step of this transformation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201912703