TY - JOUR
T1 - Native functionality in triple catalytic cross-coupling
T2 - sp3 C-H bonds as latent nucleophiles
AU - Shaw, Megan H.
AU - Shurtleff, Valerie W.
AU - Terrett, Jack A.
AU - Cuthbertson, James D.
AU - MacMillan, David W.C.
N1 - Publisher Copyright:
© 2016, American Association for the Advancement of Science. All rights reserved.
PY - 2016/6/10
Y1 - 2016/6/10
N2 - The use of sp3 C-H bonds - which are ubiquitous in organic molecules - as latent nucleophile equivalents for transition metal - catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT) and nickel catalysis, we have developed a highly selective and general C-H arylation protocol that activates a wide array of C-H bonds as native functional handles for cross-coupling. This mild approach takes advantage of a tunable HAT catalyst that exhibits predictable reactivity patterns based on enthalpic and bond polarity considerations to selectively functionalize α-amino and α-oxy sp3 C-H bonds in both cyclic and acyclic systems.
AB - The use of sp3 C-H bonds - which are ubiquitous in organic molecules - as latent nucleophile equivalents for transition metal - catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT) and nickel catalysis, we have developed a highly selective and general C-H arylation protocol that activates a wide array of C-H bonds as native functional handles for cross-coupling. This mild approach takes advantage of a tunable HAT catalyst that exhibits predictable reactivity patterns based on enthalpic and bond polarity considerations to selectively functionalize α-amino and α-oxy sp3 C-H bonds in both cyclic and acyclic systems.
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U2 - 10.1126/science.aaf6635
DO - 10.1126/science.aaf6635
M3 - Article
C2 - 27127237
AN - SCOPUS:84965013481
SN - 0036-8075
VL - 352
SP - 1304
EP - 1308
JO - Science
JF - Science
IS - 6291
ER -