Organic Letters
Letter
(16) N-methyl substitution and nitrile or nitro as resonance
stabilizing group in the bis-nucleophile did not allow the desired
annulation reaction.
G. Gontard for the XRD analyses (IPCM) Y.L. thanks the
China Scholarship Council for financial support.
(17) O’Byrne, A.; Murray, C.; Keegan, D.; Palacio, C.; Evans, P.;
Morgan, B. S. Org. Biomol. Chem. 2010, 8, 539.
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(21) Treatment of annulated products 3j and 3n with excess LDA
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This result shows the difficulty of accomplishing a double
deprotonation on this type of substrates, as the first generated
resonance-stabilized enolate undergoes a fast intramolecular carbonyl
addition, thereby impeding a second deprotonation in α position to
the keto function.
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(6) For some examples, see: (a) Giboulot, S.; Liron, F.; Prestat, G.;
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(9) For Pd-catalyzed sequences using the same bis-allylic substrate,
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8745. (b) Yoshizaki, H.; Satoh, H.; Sato, Y.; Nukui, S.; Shibasaki, M.;
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(22) The identity and the stereochemistry of compound 10r could
be unambiguously proven by X-ray diffraction of a single crystal of it
(23) We found the annulation very sensitive to proton-transfer
factors. Thus, while the N-sulfonyl bis-nucleophile-based annulations
could be achieved only in the absence of base, most of the N-alkyl-
based ones were successful only in the presence of base. In line with
this pronounced proton-transfer sensitivity, it is also remarkable that
the formal introduction of an o-bromo or o-chloro (but not an o-iodo)
substituent to the N-phenylamido ester permits base-free conditions.
(24) In the cases in which the base is not required, it is likely that the
benzoate anion, counterion of the η3-allylPd complex, acts as the base
to deprotonate the pronucleophile. See: Giambastiani, G.; Poli, G. J.
Org. Chem. 1998, 63, 9608.
(25) For a recent example, see: Chen, Y.-J.; Cai, S.-L.; Wang, C.-C.;
Cheng, J.-D.; Kramer, S.; Sun, X.-W. Chem. - Asian J. 2017, 12, 1309.
(26) (a) For a recent example, see: Shvartsbart, A.; Smith, A. B. J.
Am. Chem. Soc. 2015, 137, 3510. (b) For a review, see: Kobayashi, J.;
Kubota, T. Nat. Prod. Rep. 2009, 26, 936.
(27) (a) For a recent example, see: Scherer, M.; Bezold, D.;
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(28) (a) Kaiser, D.; Maulide, N. J. Org. Chem. 2016, 81, 4421.
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(10) (a) Furstner, A.; Feyen, F.; Prinz, H.; Waldmann, H.
̈
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Expeditious Metal-Free Access to Functionalized Polycyclic Acetals
under Mild Aqueous Conditions. Org. Lett. 2014, 16, 4284. (d) Yu, J.;
Ma, H.; Yao, H.; Cheng, H.; Tong, R. Diastereoselective and
regiodivergent oxa-[3 + 2] cycloaddition of Achmatowicz products
and cyclic 1,3-dicarbonyl compounds. Org. Chem. Front. 2016, 3, 714.
(11) For the Pd-catalyzed oxidative desymmetrization of meso-
dibenzoates of cyclic bis-allylic systems and the synthetic exploitation
of the resulting α,β-unsaturated-γ-oxycarbonyl compounds, see: Trost,
B. M.; Masters, J. T.; Lumb, J.-P.; Fateen, D. Chem. Sci. 2014, 5, 1354.
(12) For some examples of [3 + 2] C−C/N−C bond-forming
annulations, see: (a) Zhang, P.; Zhou, Y.; Han, X.; Xu, J.; Liu, H. J.
Org. Chem. 2018, 83, 3879. (b) Yuan, S.; Luo, Y.; Peng, J.; Miao, M.;
Xu, J.; Ren, H. Org. Lett. 2017, 19, 6100. (c) Narboni, N.; El Kaim, L.
Eur. J. Org. Chem. 2017, 2017, 4242. (d) Li, X.-S.; Zhao, L.-L.; Wang,
X.-K.; Cao, L.-L.; Shi, X.-Q.; Zhang, R.; Qi, J. Org. Lett. 2017, 19,
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(i) Wender, P. A.; Strand, D. J. Am. Chem. Soc. 2009, 131, 7528.
(13) Liu, Y.; Wang, X.; Xu, J.; Zhang, Q.; Zhao, Y.; Hu, Y.
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(14) (a) Jyothi, D.; Prasad, S. H. Synlett 2009, 2009, 2309.
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(15) The relative stereochemistry of the compound was ascertained
1
by H NMR NOESY and coupling constant analysis.
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