TY - JOUR
T1 - Allylmagnesium Halides Do Not React Chemoselectively because Reaction Rates Approach the Diffusion Limit
AU - Read, Jacquelyne A.
AU - Woerpel, K. A.
PY - 2017/2/17
Y1 - 2017/2/17
N2 - Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.
AB - Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.
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U2 - 10.1021/acs.joc.7b00053
DO - 10.1021/acs.joc.7b00053
M3 - Article
C2 - 28114754
AN - SCOPUS:85013176698
VL - 82
SP - 2300
EP - 2305
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 4
ER -