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. 2012 Mar 28;134(12):5528-31.
doi: 10.1021/ja3010545. Epub 2012 Mar 19.

Double-fold C-H oxygenation of arenes using PyrDipSi: a general and efficient traceless/modifiable silicon-tethered directing group

Anton V Gulevich  1 , Ferdinand S Melkonyan, Dhruba Sarkar, Vladimir Gevorgyan
Affiliations

Double-fold C-H oxygenation of arenes using PyrDipSi: a general and efficient traceless/modifiable silicon-tethered directing group

Anton V Gulevich et al. J Am Chem Soc. .

Abstract

The efficient Pd-catalyzed double-fold C-H oxygenation of arenes into resorcinols using the newly developed 2-pyrimidyldiisopropylsilyl (PyrDipSi) directing group is described. Its use allows for the sequential introduction of OAc and OPiv groups in a one-pot manner to produce orthogonally protected resorcinol derivatives. The PyrDipSi group is superior to the previously developed 2-pyridyldiisopropylsilyl (PyDipSi) group, as it is efficient for monooxygenation of ortho-substituted arenes. Notably, the PyrDipSi group can be easily installed into arene molecules and can be easily removed or modified after the oxygenation reaction.

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Figures

Scheme 1
Scheme 1
Optimization of directing group (DG)
Scheme 2
Scheme 2
Installation of PyrDipSi group
Scheme 3
Scheme 3
Nonsymetric double-fold C-H oxygenation
Scheme 4
Scheme 4
Pyvaloxylation of o-substituted PyrDipSi arenes
Scheme 5
Scheme 5
Modification of PyrDipSi group in obtained resorcinols (a) HF, 1.2 eq. AgF, MeOH/THF, rt. (b) HF, THF, 0 °C to rt, then 1.2 eq. AgF, D2O/THF, rt. (c) HF, THF rt, then 2 eq. NIS, 1.2 eq. AgF, THF, rt. (d) 1.5 eq. 4-MeOC6H4B(OH)2, 5% Pd2(dba)3, 10% PPh3, 2 eq. K3PO4, dioxane, 100 °C. (e) 1.5 eq. PyrDipSiH, 2.5% Rh2(OAc)4, 2 eq. K3PO4, dioxane, 100 °C. (f) 5% Pd(OAc)2, 2.5 eq. PhI(OPiv)2, 30% LiOAc, DCE, 80 °C. (g) HF, THF, rt, then 2 eq. NIS, 1.2 eq. AgF, THF, rt.
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