Surmounting By-Product Inhibition in an Intermolecular Catalytic Asymmetric Alkene Bromoesterification Reaction as Revealed by Kinetic Profiling

DOI: 10.14469/hpc/12349 Metadata

Created: 2023-03-07 11:49

Last modified: 2023-03-29 08:27

Author: Ben Lancaster

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Co-author: Ben Lancaster
Co-author: Christopher J Tighe
Co-author: D. Christopher Braddock


Kinetic profiling has shown that a (DHQD)2PHAL catalysed intermolecular asymmetric alkene bromoesterification reaction is inhibited by primary amides, imides, hydantoins and secondary cyclic amides, which are by-products of common stoichiometric bromenium ion sources. Two approaches to resolving the inhibition are presented enabling the (DHQD)2PHAL loading to be dropped from 10 to 1 mol% while maintaining high bromoester conversions over short reaction times. Furthermore, iterative post-reaction recrystallisations enabled a homochiral bromonaphthoate ester to be synthesised using only 1 mol% (DHQD)2PHAL.


10.14469/hpc/12352 PhCONHBr (3)
10.14469/hpc/12355 (+)-(1S,2S)-2-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl benzoate (5)
10.14469/hpc/12356 PhCONBr(t-Bu) (9)
10.14469/hpc/12357 PhCONBrMe (10)
10.14469/hpc/12358 (+)-(1S,2S)-2-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl 1-naphthoate (13)
10.14469/hpc/12359 (−)-(1S,2S)-2-Bromo-1,2,3,4-tetrahydronaphthalen-1-ol (15)
10.14469/hpc/12420 4•(Saccharin)2 (8)