Journal of the American Chemical Society
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(4) Non-metal-catalyzed carbonylations or carboxylations: (a) Ryu, I.;
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(10) Secondary alkyl chlorides and tertiary alkyl bromides were un-
reactive under these conditions. Secondary alkyl iodides were viable
substrates, albeit with decreased yields owing to their relative instabil-
ity. See the Supporting Information for details.
(11) See the Supporting Information for reaction details.
(12) (a) Stille, J. K.; Lau, K. S. Y. Acc. Chem. Res. 1977, 10, 434; (b)
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(14) A reaction with 1,1-diphenylethylene as a radical inhibitor de-
livered no carbonylation product; the mass of a radical addition prod-
uct was observed via GC-MS. See the Supporting Information for de-
tails.
(15) Loy, R. N.; Sanford, M. S. Org. Lett. 2011, 13, 2548.
(16) (a) Roth, H.; Romero, N.; Nicewicz, D. Synlett 2016, 27, 714;
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Am. Chem. Soc. 2008, 130, 511.
5 mol % Pd(PPh3)2Cl2
10 mol % IMes
2 atm CO
Br
CO2Bu
2 equiv Cs2CO3
n-heptane:n-BuOH 1:1, 50 oC, 24 h
N
N
Boc
Boc
mild, low pressure carbonylations of
unactivated alkyl bromides
70% isolated yield
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