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Asymmetric Synthesis of Fluorinated Allenes by Rhodium-Catalyzed Enantioselective Alkylation/Defluorination of Propargyl Difluorides with Alkylzincs.

Authors :
Ng JS
Hayashi T
Source :
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Sep 13; Vol. 60 (38), pp. 20771-20775. Date of Electronic Publication: 2021 Aug 24.
Publication Year :
2021

Abstract

The reaction of propargyl difluorides R <superscript>1</superscript> CF <subscript>2</subscript> C≡CR <superscript>2</superscript> with alkylzincs R <superscript>3</superscript> ZnCl giving axially chiral fluorinated allenes R <superscript>1</superscript> FC=C=CR <superscript>2</superscript> R <superscript>3</superscript> with high enantioselectivity (up to 99 % ee) was found to be catalyzed by a chiral diene/rhodium complex. A key step in the catalytic cycle is selective elimination of one of the enantiotopic fluorides at the β-position of an alkenyl-Rh intermediate, which is generated by regioselective addition of R <superscript>3</superscript> -Rh onto the triple bond of the starting difluorides.<br /> (© 2021 Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3773
Volume :
60
Issue :
38
Database :
MEDLINE
Journal :
Angewandte Chemie (International ed. in English)
Publication Type :
Academic Journal
Accession number :
34310834
Full Text :
https://doi.org/10.1002/anie.202109290