Toward Catalytic, Enantioselective
Chlorolactonization
of 1,2-Disubstituted Styrenyl Carboxylic Acids
Version 3 2017-08-24, 08:14
Version 2 2016-10-31, 14:05
Version 1 2016-08-24, 11:18
Posted on 2017-08-24 - 08:14
An investigation
into the use of Lewis base catalysis for the enantioselective
chlorolactonization of 1,2-disubstituted alkenoic acids is described.
Two mechanistically distinct reaction pathways for catalytic chlorolactonization
have been identified. Mechanistic investigation revealed that tertiary
amines predominately operate as Brønsted rather than Lewis bases.
Two potential modes of activation have been identified that involve
donation of electron density of the carboxylate to the CC
bond as well hydrogen bonding to the chlorinating agent. Sulfur- and
selenium-based additives operate under Lewis base catalysis; however,
due to the instability of the intermediate benzylic chloriranium ion,
chlorolactonization suffers from low chemo-, diastereo-, and enantioselectivities.
Independent generation of the benzylic chloriranium ion shows that
it is in equilibrium with an open cation, which leads to low specificities
in the nucleophilic capture of the intermediate.
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Denmark, Scott E.; Ryabchuk, Pavel; Burk, Matthew T.; Gilbert, Bradley B. (2016). Toward Catalytic, Enantioselective
Chlorolactonization
of 1,2-Disubstituted Styrenyl Carboxylic Acids. ACS Publications. Collection. https://doi.org/10.1021/acs.joc.6b01455
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AUTHORS (4)
SD
Scott E. Denmark
PR
Pavel Ryabchuk
MB
Matthew T. Burk
BG
Bradley B. Gilbert