Abstract
An efficient method for the selective cleavage of aryl silyl ethers is established
using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). With either 1.0 or 0.10 equivalent
of DBU, smooth desilylation of various aryl silyl ethers was accomplished selectively
in the presence of alkyl silyl ethers and other base-sensitive groups such as acetate
and ester. In addition, direct transformation of aryl silyl ethers into biaryl ethers
using a catalytic amount of DBU was possible through tandem desilylation and SN Ar reaction with activated aryl fluorides.
Key words
chemoselective - catalytic - desilylation - DBU - biaryl ether
References and Notes
<A NAME="RU11206ST-1A">1a </A>
Greene TW.
Wuts PGM.
Protective Groups in Organic Synthesis
3rd ed.:
Wiley and Sons;
New York:
1999.
<A NAME="RU11206ST-1B">1b </A>
Corey EJ.
Venkateswarlu AJ.
J. Am. Chem. Soc.
1972,
94:
6190
For reviews, see:
<A NAME="RU11206ST-2A">2a </A>
Lalonde M.
Chan TH.
Synthesis
1985,
817
<A NAME="RU11206ST-2B">2b </A>
Nelson TD.
Crouch RD.
Synthesis
1996,
1031
<A NAME="RU11206ST-2C">2c </A>
Crouch RD.
Tetrahedron
2004,
60:
5833
Representative examples on selective deprotection of silyl ether:
<A NAME="RU11206ST-3A">3a </A>
Kishore Kumar GD.
Baskaran SJ.
J. Org. Chem.
2005,
70:
4520
<A NAME="RU11206ST-3B">3b </A>
Sajiki H.
Ikawa T.
Hattori K.
Hirota K.
Chem. Commun.
2003,
654
<A NAME="RU11206ST-3C">3c </A>
Ikawa T.
Hattori K.
Sajiki H.
Hirota K.
Tetrahedron
2004,
60:
6901
<A NAME="RU11206ST-3D">3d </A>
Khan AT.
Mondal E.
Synlett
2003,
694
<A NAME="RU11206ST-3E">3e </A>
Gopinath R.
Patel BK.
Org. Lett.
2000,
2:
4177
<A NAME="RU11206ST-4">4 </A>
Collington EW.
Finch H.
Smith IJ.
Tetrahedron Lett.
1985,
26:
681
<A NAME="RU11206ST-5A">5a </A>
Jiang Z.-Y.
Wang Y.-G.
Tetrahedron Lett.
2003,
44:
3859
<A NAME="RU11206ST-5B">5b </A>
Ankala SV.
Fenteany G.
Tetrahedron Lett.
2002,
43:
4729
<A NAME="RU11206ST-5C">5c </A>
Chakraborti AK.
Sharma L.
Sharma U.
Tetrahedron
2001,
57:
9343
<A NAME="RU11206ST-5D">5d </A>
Crouch RD.
Stieff M.
Frie JL.
Cadwallader AB.
Bevis DC.
Tetrahedron Lett.
1999,
40:
3133
<A NAME="RU11206ST-5E">5e </A>
Wilson NS.
Keay BA.
Tetrahedron Lett.
1997,
38:
187
<A NAME="RU11206ST-6">6 </A>
Oyama K.-I.
Kondo T.
Org. Lett.
2003,
5:
209
<A NAME="RU11206ST-7A">7a </A>
Oediger H.
Möller F.
Eiter K.
Synthesis
1972,
591
<A NAME="RU11206ST-7B">7b </A>
Hermecz I.
Advances in Heterocyclic Chemistry
Katrizky AR.
Academic Press Inc.;
New York:
1987.
Chap. 42.
p.83
<A NAME="RU11206ST-8A">8a </A>
Yeom C.-E.
Kim YJ.
Lee SY.
Shin YJ.
Kim BM.
Tetrahedron
2005,
61:
12227
<A NAME="RU11206ST-8B">8b </A>
Yeom C.-E.
Lee SY.
Kim YJ.
Kim BM.
Synlett
2005,
1527
Known pK
a
(
DMSO) values of the protonated Lewis bases: DABCO: 8.93, proton sponge: 7.50, TMG: 13.6,
DBU: 12.0 (estimated value). For details, see:
<A NAME="RU11206ST-9A">9a </A>
Bordwell pK
a Table (acidity in DMSO): http://chem.wisc.edu/areas/reich/pkatable (accessed July
2006).
<A NAME="RU11206ST-9B">9b </A>
David Evans research group: http://daecr1.harvard.edu/pKa/pka.html (accessed July
2006).
<A NAME="RU11206ST-10">10 </A> This trend corresponds to the report on the susceptibility of silylated cresols
to basic hydrolysis, which was examined using 5% NaOH in 95% MeOH:
Davies JS.
Higginbotham CL.
Tremeer EJ.
Brown C.
Treadgold RC.
J. Chem. Soc., Perkin. Trans. 1
1992,
3043
<A NAME="RU11206ST-11A">11a </A>
Rao AV.
Gurjar MK.
Reddy KL.
Rao AS.
Chem. Rev.
1995,
92:
2135
<A NAME="RU11206ST-11B">11b </A>
Nicolaou KC.
Boddy CNC.
J. Am. Chem. Soc.
2002,
124:
10451
<A NAME="RU11206ST-12">12 </A>
Cotter RJ.
Engineering Plastics: A Handbook of Polyaryl Ethers
Gordon and Breach;
Langhorne, PA:
1995.
<A NAME="RU11206ST-13">13 </A>
The nitro-substituted aryl fluorides were chosen as representative substrates, and
we found that aromatic fluorides substituted with other electron-withdrawing groups,
such as cyano or formyl, were also effective. The results will be described in a full
account.
<A NAME="RU11206ST-14">14 </A>
Cleavage of Aryl Silyl Ethers (Table 3, Entry 2); Typical Procedure : To a magnetically stirred solution of tert -butyldimethyl(2-naphthalenyloxy)silane (460 mg, 1.78 mmol) in anhyd MeCN (3.4 mL)
and H2 O (0.18 mL) was added DBU (0.26 mL, 1.78 mmol). After the starting material disappeared
(TLC), sat. aq NH4 Cl solution (5 mL) was poured into the reaction mixture. The mixture was extracted
with CH2 Cl2 (2 × 5 mL), and the organic layer was collected, dried over MgSO4 , filtered, and concentrated under reduced pressure. The resulting residue was purified
further by passing through a short silica gel column (ca 5 cm) and after vacuum evaporation
pure 2-naphthol was obtained (250 mg, 98% yield). Desilylated position of bissilyl
ether was determined by the chemical shift difference of the free alcohol or alkyl
substituents on silicon in NMR. Generally, the chemical shifts of aryl alcohols are
higher than those of the aliphatic alcohols and alkyl substituent of aryl silyl ethers
also exhibited more downfield signals in 1 H and 13 C NMR than those of aliphatic ones.
<A NAME="RU11206ST-15">15 </A>
Tandem, One-Pot Biaryl Ether Formation (Table 5, Entry 2); Typical Procedure : To a magnetically stirred solution of tert -butyldimethyl-(4-methoxyphenoxy)silane (410 mg, 1.73 mmol) in anhyd DMSO (3.5 mL)
and H2 O (4 µL) were added p -fluoronitrobenzene (152 µL, 1.44 mmol), and DBU (13 µL, 0.173 mmol) sequentially
at r.t. The mixture was heated to 80 °C, and the stirring was continued until the
aryl fluoride disappeared on TLC. After completion of the reaction, the mixture was
partitioned between Et2 O (5 mL) and brine (5 mL), and the organic layer was separated, dried over MgSO4 , filtered, and concentrated under reduced pressure. The residue was purified through
silica gel column chromatography (n -hexane-EtOAc = 6:1) to afford the desired pure biaryl ether (320 mg, 91% yield).