Journal of the American Chemical Society
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(16) Rh-catalyzed reductive Claisen rearrangement and discussions
about the functional group compatibility of the IrelandꢀClaisen re-
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(17) Discussions about the functional group compatibility of the
JohnsonꢀClaisen rearrangement:(a) Cosgrove, K. L.; McGeary, R. P.
Synlett 2009, 1749–1752. (b) Cosgrove, K. L.; McGeary, R. P. Tetra-
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(3) The regioselectivity in Pd-catalyzed allylic substitutions thatinvolve
a (π-allyl)palladium intermediate is highly dependent on the substitution
pattern of allylic substrates. See refs 1 and 2aꢀ2i.
(4) Rh-catalyzed R-selective allylic alkylations of copper enolates
derived from aryl ketones with chiral secondary allylic alcohol derivatives
bearing aterminalalkene moiety:(a)Evans, P. A.; Leahy, D. K. J. Am. Chem.
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(5) Rh-catalyzed allylic substitution of allylic carbonates having allylic
system in the internal position with enoxysilanes occurred competitively at
the R- and γ-positions:Muraoka, T.; Matsuda, I.; Itoh, K. Tetrahedron. Lett.
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(6) Rh-catalyzed R-selective allylic alkylations of malonates with
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(8) Fe-catalyzed R-selective allylic alkylations of soft carbon nucleo-
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(19) Unsymmetrically substituted secondary allylic bromides and
chlorides are not suitable as substrate because halogenation of the
corresponding allylic alcohols is not regioselective. While almost no
reaction occurred with a primary allylic bromide, a primary allylic
chloride underwent the reaction in a poor product yield with a moderate
R-selectivity.
(20) Reaction of 1a with methyl isobutyrate-derived ketene silyl
acetal resulted in low conversion (35%) and poor yield (13%). The use
of propionate-derived bis-trimethylsilyl ketene acetal resulted in no
reaction.
(21) The observed stereochemical outcome can be rationalized by
the anti-attack of the copper enolate to the allyic phosphates in a
conformation that avoids the A1,3-strain. See also refs 11a,11b.
(22) The stereochemistry of the R-isomer has not been analyzed.
(23) (a) Yoshikai, N.; Zhang, S.-L.; Nakamura, E. J. Am. Chem. Soc.
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(10) Pd-catalyzed γ-selective and stereospecific allylꢀaryl coupling
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(11) Cu-catalyzed γ-selective and stereospecific allylꢀalkyl and al-
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bori, U.; Makida, Y.; Sawamura, M. J. Am. Chem. Soc. 2010,
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2010, 12, 2438–2440. Cu-catalyzed conjugate additions of alkylboron
compounds (alkyl-9-BBN) to imidazol-2-yl R,β-unsaturated ketones:(c)
Ohmiya, H.; Yoshida, M.; Sawamura, M. Org. Lett. 2011, 13, 482–485. Cu-
catalyzed carboxylations of alkylboron compounds (alkyl-9-BBN) with
carbon dioxide:(d) Ohmiya, H.; Tanabe, M.; Sawamura, M. Org. Lett.
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(12) Reviews on Cu-catalyzed allylic substitutions:(a) Hoveyda,
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(13) Transmetalation between Cu(I) complexes and ketene silyl
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