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Scheme 5. α-Boryl Substitution Enhances Reaction Rate
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a
Yield determined by GC using dodecane as an internal standard. Ar =
4-methoxyphenyl.
increase in the stability of the intermediate radical. It has been
shown that a neighboring boron atom can offer significant
radical stability on the order of 14.5 kcal/mol.21
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In summary, we created a mild, low-cost reaction system for
the general borylation of alkyl halides. The reaction generally
proceeds in high yields with exceptional substrate scope.
Consequently, the reaction should be the first choice for those
seeking to borylate alkyl halides. The target reaction also offers
the first synthetically useful control over direct borylation vs
radical ring-closing or ring-opening reactions using temper-
ature. Further efforts will be directed toward understanding the
reaction mechanism of this interesting transformation.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
(21) Grotewold, J.; Lissi, E. A.; Scaiano, J. C. J. Organomet. Chem.
1969, 19, 431.
Experimental details and spectroscopic data (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge funds from Indiana University in partial
support of this work. We also gratefully acknowledge the
American Chemical Society Petroleum Research Fund
(PRF52233-DNI1) and the NSF CAREER Award (CHE-
1254783). Eli Lilly & Co. and Amgen supported this work
through the Lilly Grantee Award and the Amgen Young
Investigator Award.
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