TY - JOUR
T1 - A Diverted Aerobic Heck Reaction Enables Selective 1,3-Diene and 1,3,5-Triene Synthesis through C-C Bond Scission
AU - McAlpine, Neil J.
AU - Wang, Long
AU - Carrow, Brad P.
N1 - Funding Information:
Financial support was provided by Princeton University and NIH R35GM128902.
PY - 2018/10/24
Y1 - 2018/10/24
N2 - Substituted 1,3-dienes are valuable synthetic intermediates used in myriad catalytic transformations, yet modern catalytic methods for their preparation in a highly modular fashion using simple precursors are relatively few. We report here an aerobic boron Heck reaction with cyclobutene that forms exclusively linear 1-aryl-1,3-dienes using (hetero)arylboronic acids, or 1,3,5-trienes using alkenylboronic acids, rather than typical Heck products (i.e., substituted cyclobutenes). Experimental and computational mechanistic data support a pericyclic mechanism for C-C bond cleavage that enables the cycloalkene to circumvent established limitations associated with diene reagents in Heck-type reactions.
AB - Substituted 1,3-dienes are valuable synthetic intermediates used in myriad catalytic transformations, yet modern catalytic methods for their preparation in a highly modular fashion using simple precursors are relatively few. We report here an aerobic boron Heck reaction with cyclobutene that forms exclusively linear 1-aryl-1,3-dienes using (hetero)arylboronic acids, or 1,3,5-trienes using alkenylboronic acids, rather than typical Heck products (i.e., substituted cyclobutenes). Experimental and computational mechanistic data support a pericyclic mechanism for C-C bond cleavage that enables the cycloalkene to circumvent established limitations associated with diene reagents in Heck-type reactions.
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U2 - 10.1021/jacs.8b10007
DO - 10.1021/jacs.8b10007
M3 - Article
C2 - 30289691
AN - SCOPUS:85055119320
VL - 140
SP - 13634
EP - 13639
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 42
ER -