Subscribe to RSS
DOI: 10.1055/s-0031-1290205
Copper(II)-Catalyzed O-Arylation of Tertiary Alcohols with Arylbismuth(III) Reagents: A Convenient System for Aryl Transfer
Publication History
Publication Date:
25 January 2012 (online)
![](https://www.thieme-connect.de/media/synlett/201203/lookinside/thumbnails/10.1055-s-0031-1290205-1.jpg)
Abstract
Copper(II)-catalyzed O-arylation of tertiary alcohols with various triarylbismuth reagents was investigated. A convenient and efficient system for aryl ether formation of tertiary alcohols has been developed through the in situ oxidation of stable triarylbismuth(III) to triarylbismuth(V) species using PhI(OAc)2 as the oxidant in the presence of a catalytic amount of copper(II) acetate.
Key words
O-phenylation - O-arylation - arylbismuth - ether - iodobenzene diacetate - tertiary alcohol
-
1a
Evans DA.Wood MR.Trotter BW.Richardson TI.Barrow JC.Katz JL. Angew. Chem. Int. Ed. 1998, 37: 2700 -
1b
Nicolaou KC.Mitchell HJ.Jain NF.Winssinger N.Hughes R.Bando T. Angew. Chem. Int. Ed. 1999, 38: 240 -
1c
Cao B.Park H.Joullié MM.
J. Am. Chem. Soc. 2002, 124: 520 -
1d
Joullié MM.Richard DJ. Chem. Commun. 2004, 2011 -
2a
Pietri S.Liebgott T.Finet J.-P.Culcasi M.Billottet L.Bernard-Henriet C. Drug Dev. Res. 2001, 54: 191 -
2b
Brands KMJ.Dolling U.-H.Jobson RB.Marchesini G.Reamer RA.Williams JM. J. Org. Chem. 1998, 63: 6721 -
2c
Nicolaou KC.Sarlah D.Wu TR.Zhan W. Angew. Chem. Int. Ed. 2009, 48: 6870 - For reviews, see:
-
3a
Finet J.-P. Chem. Rev. 1989, 89: 1487 -
3b
Ley SV.Thomas AW. Angew. Chem. Int. Ed. 2003, 42: 5400 -
4a
Barton DHR.Finet J.-P.Khamsi J.Pichon C. Tetrahedron Lett. 1986, 27: 3619 -
4b
Barton DHR.Charpiot B.Motherwell WB. Tetrahedron Lett. 1982, 23: 3365 -
4c
Barton DHR.Finet J.-P.Pichon C. J. Chem. Soc., Chem. Commun. 1986, 65 -
4d
Barton DHR.Finet J.-P.Khamsi J. Tetrahedron Lett. 1987, 28: 887 -
4e
The reaction can be also carried out under air as long as moisture is excluded.
-
5a
Finet J.-P.Fedorov AY. J. Organomet. Chem. 2006, 691: 2386 -
5b
Combes S.Finet J.-P. Tetrahedron 1998, 54: 4313 -
6a
Ikegai K.Fukumoto K.Mukaiyama T. Chem. Lett. 2006, 35: 612 -
6b
Mukaiyama T.Sakurai N.Ikegai K. Chem. Lett. 2006, 35: 1140 -
6c
Sakurai N.Ikegai K.Mukaiyama T. ARKIVOC 2007, (vii): 254 - 7
Sheppard GS. Synlett 1999, 1207 -
8a
Matano Y.Aratani Y.Miyamatsu T.Kurata H.Miyaji K.Sasako S.Suzuki H. J. Chem. Soc., Perkin Trans. 1 1998, 2511 -
8b
Suzuki H.Ogawa T.Komatsu N.Matano Y.Murafuji T.Ikegami T. Organobismuth Chemistry Elsevier; Amsterdam: 2001.
References and Notes
Triphenylbismuth(V) diacetate(1a) is commercially available from Tokyo Kasei Kogyo, Inc. and used without purification. Triarylbismuth(V) diacetates 1b-i were readily prepared from BiCl3 as described below.5a,8a,¹¹,¹²
10
Synthesis of Triarylbismuth
7b-i:
Method A for the
Synthesis of Compounds 7e,i
To a mixture of n-BuLi (9.7 mmol, 1.6 M in hexane) and N,N,N′,N′-tetramethylethylenediamine
(9.7 mmol) was added dropwise to a solution of the methoxymethoxy-benzene
(9.1 mmol) in anhyd THF (18 mL) at 0 ˚C. After stirring
for 6 h at this temperature, a THF solution (9 mL) of BiCl3 (2.9
mmol) was added slowly at -35 ˚C. The
reaction mixture was allowed to warm to r.t., quenched with H2O
(30 mL), extracted with EtOAc (2 × 20 mL), and the combined organic
layers were washed with brine and dried over Na2SO4.
The solvent was removed under reduced pressure, and the residue
was purified by column chromatography on silica gel using hexane-EtOAc
or recrystallization from MeOH to give the corresponding triarylbismuth(III).
Method B for the Synthesis of Compounds 7b-d,f-h
To
an anhyd THF solution (17 mL) of arylmagnesium bromide, prepared
from Mg (17 mmol) and aryl bromide (17.5 mmol), was added a THF
solution (5 mL) of BiCl3 (5 mmol) at 0 ˚C.
The reaction mixture was allowed to warm to r.t., quenched with
H2O (30 mL), extracted with EtOAc (2 × 20 mL),
and the combined organic layers were washed with brine and dried
over Na2SO4. The solvent was removed under
reduced pressure, and the residue was purified by column chromatography
on silica gel using hexane-EtOAc or recrystallization from
MeOH to give the corresponding triarylbismuth(III).
Synthesis of Triarylbismuth
Diacetate 1b-i
Method A for the Synthesis of Compounds 1c-f,i
A
mixture of NaBO3˙H2O (4.2 mmol) and
Ar3Bi(III) (1.4 mmol) in AcOH (14 mL) was stirred at
r.t. for 30 min. The resulting mixture was poured into H2O
(50 mL) and was extracted with CH2Cl2 (2 × 30
mL). The combined organic layers were washed with H2O
(2 × 30 mL) and dried over MgSO4. The solvent
was distilled off, and the crude product was precipitated from a
mixture of CH2Cl2 (1 mL)-hexane (30
mL) to give the corresponding triarylbismuth(V) diacetate.
Method
B for the Synthesis of Compounds 1b,g,h
A mixture
of Ar3Bi(III) (1.4 mmol) and PhI(OAc)2 (1.5 mmol)
in CH2Cl2 (14 mL) was stirred under argon atmosphere
for 24 h at r.t. The solvent was distilled off, and the crude product
was precipitated from a mixture of CH2Cl2 (1
mL)-hexane (30 mL) to give the corresponding triarylbismuth(V)
diacetate.
A related one-pot but not in situ copper(II)-catalyzed N-arylation of anilines was reported by Combes and Finet.5b Barton et al. found that copper(II)-catalyzed N-phenylation of amines by Ph3Bi(III) occurs smoothly.4d
13
Typical Procedure
for the O-Arylation of 2 (Table 3, entry 5)
To a suspension
mixture of alcohol 2 (0.22 mmol), Cy2NMe (0.43
mmol), and powdered MS4A (250 mg) in CH2Cl2 (1 mL)
was added Cu(OAc)2 (0.01 mmol). After the mixture was
stirred for 30 min, Ar3Bi (0.33 mmol) and PhI(OAc)2 (0.41
mmol) were added, and the resulting mixture was kept stirring at
r.t. under an oxygen atmosphere (1 atm). Upon completion of the
reaction (monitored by TLC), 10% aq NH3 solution
(2 mL) was added to the mixture. The precipitates were filtered
off, and the filtrate was extracted with CH2Cl2 (2 × 10
mL). The combined extracts were washed with brine, dried over Na2SO4,
and concentrated under reduced pressure to give an oily residue.
Purification by column chromatog-raphy on silica gel using hexane-EtOAc
yielded the corresponding aryl ether 3
¹4 or 4.
Spectral Data
for the Representative Products 3c,f
Benzyl
2-Methyl-2-(3-methylphenoxy)propionate (3c)
Yield:
60 mg (98%). Colorless oil. IR (neat): 2936, 1733, 1488,
1280, 1175, 1137, 959, 695 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 1.60 (6 H,
s, Me), 2.22 (3 H, s, tolyl), 5.21 (2 H, s, Bn), 6.57 (1 H, br d, J = 8.0 Hz,
H6′), 6.61 (1 H, br s, H2′), 6.78 (1 H, br d, J = 7.6 Hz,
H4′), 7.05 (1 H, dd, J = 8.0,
7.6 Hz, H5′), 7.27-7.33 (5 H, m, Bn). ¹³C
NMR (100 MHz, CDCl3): δ = 21.5, 25.6,
67.1, 79.1, 115.9, 120.0, 123.0, 128.4, 128.5, 128.6, 128.9, 135.6,
139.3, 153.4, 174.3. HRMS (ESI-FT): m/z calcd
for C18H20O3Na: 307.1310 [M + Na]+;
found: 307.1307.
Benzyl 2-[3-(Methoxymethoxy)phenoxy]-2-methyl-propanoate
(3f)
Yield: 130 mg (83%). Colorless oil.
IR (neat): 2938, 1731, 1600, 1486, 1282, 1138, 1017, 851, 696 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 1.61 (6 H,
s, Me), 3.45 (3 H, s, OMe), 5.09 (2 H, s, OCH2O), 5.20
(2 H, s, Bn), 6.40 (1 H, ddd, J = 8.0, 2.3,
0.9 Hz, H6′), 6.57 (1 H, dd, J = 2.3,
2.3 Hz, H2′), 6.66 (1 H, ddd, J = 8.3,
2.3, 0.9 Hz, H4′), 7.06 (1 H, dd, J = 8.3, 8.0
Hz, H5′), 7.27-7.45 (5 H, m, Bn). ¹³C
NMR (100 MHz, CDCl3): δ = 25.5, 56.1,
67.2, 79.3, 94.6, 107.7, 110.1, 112.2, 128.4, 128.6, 129.6, 135.6,
156.6, 158.3, 174.2. HRMS (ESI-FT): m/z calcd
for C19H22O5Na: 353.1365 [M + Na]+; found:
353.1361.