Palladium-catalyzed hydroxymethylation of aryl-and heteroarylboronic acids using aqueous formaldehyde

Article abstract of DOI:10.1002/adsc.201400845

Cyclometallated NHC palladium complexes prepared from palladium(II) acetate [Pd(OAc)2] and unsymmetrical 1,3-diarylimidazolinium salts catalyzed the hydroxymethylation of (hetero)arylboronic acids using an excess amount of formalin to afford (hetero)arylm

Full text of DOI:10.1002/adsc.201400845

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DOI: 10.1002/adsc.201400845
Palladium-Catalyzed Hydroxymethylation of Aryl- and
Heteroarylboronic Acids using Aqueous Formaldehyde
Tetsuya Yamamoto,a,b,* Azamat Zhumagazin,a Takuma Furusawa,a Ryoji Tanaka,c
Tetsu Yamakawa,a,* Yohei Oe,b and Tetsuo Ohtab,*
a
Catalysis Group, Sagami Chemical Research Institute, Hayakawa 2743-1, Ayase, Kanagawa 252-1193, Japan
E-mail: t-yamamoto@sagami.or.jp or t_yamakawa@sagami.or.jp
Department of Biomedical Information, Faculty of Life and Medical Sciences, Doshisha University, Kyotanabe, Kyoto
b
610-0394, Japan
E-mail: tota@mail.doshisha.ac.jp
Instrumental Analysis Group, Sagami Chemical Research Institute, Hayakawa 2743-1, Ayase, Kanagawa 252-1193, Japan
c
Received: August 26, 2014; Revised: October 6, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400845.
Abstract: Cyclometallated NHC palladium com-
plexes prepared from palladium(II) acetate
[Pd(OAc)2] and unsymmetrical 1,3-diarylimidazoli-
nium salts catalyzed the hydroxymethylation of
(hetero)arylboronic acids using an excess amount of
formalin to afford (hetero)arylmethanols in good to
satisfactory yields.
a wide range of functional groups, it requires an
excess amount of expensive metallic reagents.
Transition metal-catalyzed 1,2-addition of organo-
boron compounds to carbonyl compounds is tolerant
to a wide range of functional groups.[10–13] However,
only the reactions using aldehydes except formalde-
hyde have been reported. This stimulated us to inves-
tigate the transition metal-catalyzed 1,2-addition of
organoboron compounds to formaldehyde or its
equivalents, as candidate for a new synthetic route to
(hetero)arylmethanols. As a preliminary investigation,
we examined the hydroxymethylation of naphthalen-
2-ylboronic acid 1a using aqueous formaldehyde in
the presence of iron,[13j] cobalt,[13f] rhodium[11i] and
copper[13i] catalysts; these catalysts are effective in the
Keywords: 1,2-addition; cyclometallated palladium
complexes; formaldehyde; N-heterocyclic carbenes;
palladium catalyst
Regioselective hydroxymethylation on the (hetero)ar- addition of arylboronic acids to aliphatic and aromatic
omatic rings provides directly (hetero)arylmethanols aldehydes. Nevertheless, these catalysts afforded very
which are important intermediates in various applica- low yields of naphthalen-2-ylmethanol 2a under the
tions such as bioactive compounds,[1] fluorescent previously reported reaction conditions as shown in
probes[2] and functionalized polymers.[3] So far, (heter- Scheme 1. In contrast, phosphapalladacycle 3, which
o)arylmethanols have been synthesized via three also revealed high catalytic activity in the addition of
routes. The first route is the addition of (hetero)aryl- arylboronic acids to aldehydes,[11e] provided the de-
lithium or magnesium reagents to formaldehyde or its sired product in 56% yield.
equivalents.[4] This route has restriction in usable
The results in Scheme 1 suggest that strong elec-
functional groups due to the high reactivity of organo- tron-donating ligand coordinated palladacycle com-
lithium or magnesium reagents. The second route is plexes can be effective in this nucleophilic addition. It
the palladium-catalyzed formylation of (hetero)aryl is well known that most of the N-heterocyclic carbene
halides followed by the reduction of the formyl (NHC) ligands are stronger electron donors than
group.[5,6] In this route, the formylation must frequent- phosphine ligands.[14] Therefore, we envisaged that the
ly be performed under a high-pressure carbon monox- use of NHCs instead of the phosphorus ligand of the
ide atmosphere. Recently, the palladium-catalyzed phosphapalladacycle would improve the catalytic ac-
cross-coupling of aryl halides and hydroxymethyltin,[7] tivity in the palladium-catalyzed hydroxymethylation
acyloxyzinc[8] or boron[9] reagents has been developed in Scheme 1. Herein we report the direct hydroxyme-
as the third route; the hydrolysis of acyloxy group is thylation of (hetero)arylboronic acids using aqueous
necessary after the reactions with the latter two met- formaldehyde with a newly synthesized cyclometallat-
allic reagents. Although this route is tolerant to ed NHC palladium complex.
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Tetsuya Yamamoto et al.
5a–d exhibited remarkable catalytic activity compared
to phosphapalladacycle 3. (Table 1 vs. Scheme 1).
Complex 5a provided the corresponding alcohol in
89% yield with 0.3 mol% catalyst loading (entry 2).
Furthermore, methyl-, bromo- or phenylthio-substitut-
ed NHC coordinated complexes 5b–d showed out-
standing catalytic activity with 0.1 mol% catalyst
loading (entries 3–5). Particularly, turnover numbers
of palladium atom obtained with 5d reached 960
(entry 5). The reaction with 5d at 708C provided only
Table 1. 5a-d-catalyzed hydroxymethylation of naphthalen-2-
ylboronic acid 1a.
Scheme 1. Transition metal-catalyzed hydroxymethylation.
We examined the synthesis and the isolation of cy-
clometallated NHC palladium(II) complexes from
imidazolium salts 4a–d. As a result, cyclometallated
NHC palladium(II) complexes 5a–d were synthesized
from Pd(OAc)2 as a Pd(II) precursor, a small excess
of imidazolium salts 4a–d and a small amount of
Entry
Complex 5
x
Yield [%][a]
1
2
3
4
5a
5a
5b
5c
5d
5d
5d
0.1
0.3
0.1
0.1
0.1
0.1
0.1
61
89
93
91
À
sodium acetate via C H bond cleavage orthopallada-
tion (Scheme 2). X-Ray crystallographic analysis[15]
and/or high-resolution FAB mass spectroscopy re-
vealed that each of the complexes are a m-chloro-
bridged dimer and that Pd is divalent. The complex
5c has a contamination of 5a about 5% that is attrib-
uted to a debromination of 4c by a small amount of
Pd(0) generated from Pd(OAc)2 and NHC.[16]
5
96
6[b]
7[c]
92 (88)[d]
52
[a]
1
Determined by H NMR with diphenylmethane as an in-
ternal standard.
The reaction temperature was 708C.
The reaction temperature was 508C.
Isolated yield.
[b]
[c]
[d]
In the hydroxymethylation of naphthalen-2-ylbor-
onic acid 1a with aqueous formaldehyde, complexes
À
Scheme 2. Synthesis of cyclometallated NHC palladium(II) complexes 5a–d via C H bond cleavage orthopalladation.
2
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Hydroxymethylation of Aryl- and Heteroarylboronic Acids
Table 2. The optimization of the reaction conditions for the
5d-catalyzed hydroxymethylation of naphthalen-2-ylboronic
acid 1a.
Table 3. 5d-catalyzed hydroxymethylation of several (heter-
o)arylboronic acids.
Entry
Solvent
Base
Yield [%][a]
1
2
3
4
5
6
7
8
9
10
THF
THF
THF
THF
CsF
K2CO3
KF
K3PO4
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
85
76
78
81
69
87
67
39
23
28
Entry Ar
1
x
Yield [%][a]
1
1-naphthyl
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
0.2 76
0.1 88
0.2 90
0.5 76
0.1 82
0.1 75
0.1 83
0.3 88
0.05 69
0.3 80
0.1 91
2
4-methoxyphenyl
THF
3
2-methoxyphenyl
2-Me-THF
toluene
ethanol
DMSO
DMF
4
5
3,5-bis(trifluoromethyl)phenyl
4-chlorophenyl
6
4-bromophenyl
7
4-benzoylphenyl
8
9
4-(ethoxycarbonyl)phenyl
4-formyl-3-methoxyphenyl
3-cyanophenyl
3-nitrophenyl
2-(methoxycarbonyl)phenyl
2-benzofuranyl
2-benzo[b]thiophenyl
2-(BocNH)phenyl
2,6-dimethoxy-3-pyridyl
[a]
Isolated yield.
10[b]
11
12[c]
13
14[c]
15[c]
16
2
30
0.1 73
0.5 87
0.1 78
0.3 79
a slight decrease in the yield (entry 6), while the yield
was remarkably low at 508C (entry 7). Therefore, all
the reactions hereinafter under various conditions
were carried out at 708C to consider safety.
The optimization of the reaction conditions for the
5d-catalyzed hydroxymethylation of naphthalen-2-yl-
boronic acid 1a is summarized in Table 2. By the use
of CsF, the corresponding product 2a was obtained in
excellent yields (entry 1), while potassium or sodium
salts such as K2CO3, KF, K3PO4 and Na2CO3 were less
[a]
Isolated yield.
[b]
2-Me-THF was used instead of THF. The reaction was
carried out at 858C.
CsF was used instead of Cs2CO3.
[c]
effective than cesium salts for this hydroxymethyla- good to excellent yields under 0.05–0.3 mol% catalyst
tion (entries 2–5). The yield with the use of 2-methyl- loading (entries 5–11 and 15). Moreover, an addition
tetrahydrofuran (2Me-THF) instead of THF remained of arylboronic acid to a formyl group on the aromatic
virtually the same (entry 6). The yield was declined to ring did not occur (entry 9). Heteroarylboronic acids
69% in toluene as solvent (entry 7). Polar solvents such as pyridyl-, benzofuranyl- and benzothiophenyl-
such as ethanol, DMSO and DMF were not effective boronic acids gave the corresponding alcohols in good
for the reaction (entries 8–10).
yields (entries 13, 14 and 16). Naphthalen-1-ylboronic
The scope and limitations of the 5d-catalyzed hy- acid and sterically bulky (hetero)arylboronic acids
droxymethylation of (hetero)arylboronic acids with which have methoxy or (tert-butoxycarbonyl)amino
various functional groups are summarized in Table 3. groups in the ortho-position were also converted to
Electron-rich arylboronic acids were converted to the thecorresponding alcohols in good yields (entries 1, 3,
corresponding arylmethanols in excellent yields with 15 and 16). The hydroxymethylation of 2-(methoxy-
low catalyst loading (entries 2, 3 and 15), although carbonyl)phenylboronic acid 1n which has an elec-
electron-poor arylboronic acid such as 3,5-bis(tri- tron-withdrawing group in the ortho-position afforded
ACHTUNGTRENNUNG
ly with substrates having various reactive functional At first, the insertion of formaldehyde into the
groups such as carbamate, chloro, bromo, benzoyl, carbon-palladium bond of arylpalladium(II) inter-
ethoxycarbonyl, formyl, cyano and nitro groups in mediate 6, which is generated by the transmetallation
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The test tube was evacuated and backfilled with argon. This
sequence was repeated five times. Then THF (0.5 mL) and
37 wt% formaldehyde in H2O (102 mg, formaldehyde
1.25 mmol) were added via the rubber septum with syringe.
In an argon flow, the rubber septum was replaced with
a Teflon liner screw cap. The sealed test tube was placed
into an oil bath preheated at 708C. After the reaction mix-
ture had been stirred for 2 h, the reaction mixture was
cooled to room temperature. The obtained crude material
was purified by passing it through a silica gel column with
hexane/ethyl acetate.
Acknowledgements
We thank Prof. Inoue and Ms. Ishikawa, Tokyo Institute of
Technology, for the HR-MS measurements.
Scheme 3. Possible catalytic cycle.
References
between arylboronic acid 1 and the cyclometallated
NHC palladium(II) complex 5, forms the palladi-
[1] a) H. Y. Hung, E. Ohkoshi, M. Goto, K. F. Bastow, K.
Nakagawa-Goto, K. H. Lee, J. Med. Chem. 2012, 55,
5413–5424; b) M. Liu, W. Zhang, J. Wei, X. Lin, Mar.
Drugs 2011, 9, 1554–1565; c) A. M. Palmer, V. Chiesa,
A. Schmid, G. Mꢁnch, B. Grobbel, P. J. Zimmermann,
C. Brehm, W. Buhr, W.-A. Simon, W. Kromer, S. Pos-
tius, J. Volz, D. Hess, J. Med. Chem. 2010, 53, 3645–
3674; d) L. Xie, D. Yu, C. Wild, G. Allaway, J. Turpin,
P. C. Smith, K. H. Lee, J. Med. Chem. 2004, 47, 756–
760.
[2] a) M. Strianese, S. Milione, V. Bertolasi, C. Pellecchia,
Inorg. Chem. 2013, 52, 11778–11786; b) T. Mukherjee,
J. C. Pessoa, A. Kumar, A. R. Sarkar, Dalton Trans.
2012, 41, 5260–5271.
[3] a) R. K. Roy, S. Ramakrishnan, Macromolecules 2011,
44, 8398–8406; b) N. L. Morozowich, A. L. Weikel, J. L.
Nichol, C. Chen, L. S. Nair, C. T. Laurencin, H. R. All-
cock, Macromolecules 2011, 44, 1355–1364; c) T.
Yamada, M. Suginome, Macromolecules 2010, 43,
3999–4002.
ACHTUNGTRENNUNGum(II) alkoxide 7. Successively, Pd complex 7 is hy-
drolyzed to give the corresponding arylmethanol and
the palladium(II) hydroxide 8. Finally, transmetalla-
tion between arylboronic acid 1 and palladium(II) hy-
droxide 8 regenerates an arylpalladium(II) intermedi-
ate 6.
In conclusion, we have developed the cyclometal-
lated NHC palladium complexes that catalyze the
direct hydroxymethylation of aryl- and heteroarylbor-
onic acids using aqueous formaldehyde as readily
available C1 source to give the corresponding various-
ly functionalized (hetero)arylmethanols. The cyclome-
tallated NHC palladium complexes have been readily
synthesized from palladium acetate and imidazolini-
um salts and exhibit high turnover numbers in this hy-
droxymethylation.
[4] L. Miginiac, in: Handbook of Grignard Reagents, (Eds.:
G. S. Silverman, P. E. Rakita), Marcel Dekker, New
York, 1996, pp 361–372.
Experimental Section
General Procedure for the Synthesis of Palladium(II)
Complex 5a–d
[5] For selected reviews: a) X.-F. Wu, H. Neumann, M.
Beller, Chem. Rev. 2013, 113, 1–35; b) X.-F. Wu, H.
Neumann, M. Beller, ChemSusChem 2013, 6, 229–241;
c) A. Brennfuehrer, H. Neumann, M. Beller, Angew.
Chem. 2009, 121, 4176–4196; Angew. Chem. Int. Ed.
2009, 48, 4114–4133; d) T. Morimoto, K. Kakiuchi,
Angew. Chem. 2004, 116, 5698–5706; Angew. Chem.
Int. Ed. 2004, 43, 5580–5588.
[6] For selected recent examples: a) K. Natte, A. Dumrath,
H. Neumann, M. Beller, Angew. Chem. 2014, 126,
10254–10258; Angew. Chem. Int. Ed. 2014, 53, 10090–
10094; b) T. Ueda, H. Konishi, K. Manabe, Angew.
Chem. Int. Ed. 2013, 52, 8611–8615; c) T. Ueda, H. Ko-
nishi, K. Manabe, Org. Lett. 2013, 15, 5370–5373;
d) A. V. Gadakh, D. Chikanna, S. S. Rindhe, B. K.
Karale, Synth. Commun. 2012, 42, 658–666; e) T. Ueda,
H. Konishi, K. Manabe, Org. Lett. 2012, 14, 3100–3103;
f) T. Fujihara, T. Hosoki, Y. Katafuchi, T. Iwai, J.
Under an argon atmosphere, a 100-mL Schlenk flask was
charged with palladium acetate (1.0 equiv.), imidazolinium
salt 4 (1.3 equiv.), sodium acetate (0.3 equiv.) and anhydrous
1,4-dioxane. The reaction mixture was stirred at 1008C for
2 h and then cooled to room temperature. After the solvent
was removed completely, the residue was passed through
a short pad of silica gel with CH2Cl2 and was purified by re-
crystallization from CH2Cl2/Et2O or CH2Cl2/MeOH to
afford the palladium complex 5.
General Procedure for the Hydroxymethylation of
(Hetero)Arylboronic Acids
5d
(0.000125–0.005 mmol),
(hetero)arylboronic
acid
(0.50 mmol) and inorganic base (1.0 mmol) were charged in
a 10-mL screw-top test tube sealed with a rubber septum.
4
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COMMUNICATIONS
Hydroxymethylation of Aryl- and Heteroarylboronic Acids
Terao, Y. Tsuji, Chem. Commun. 2012, 48, 8012–8014.
Recently, Ryu et al. investigated the radical mediated
hydroxymethylation of aryl halides under high-pressure
carbon monoxide, see: g) T. Kawamoto, T. Okada, D. P.
Curran, I. Ryu, Org. Lett. 2013, 15, 2144–2147.
Tetrahedron 2010, 66, 6814–6819; e) Y. Suzuma, S. Hay-
ashi, T. Yamamoto, Y. Oe, T. Ohta, Y. Ito, Tetrahedron:
Asymmetry 2009, 20, 2751–2758; f) M. Kuriyama, N.
Ishiyama, R. Shimazawa, R. Shirai, O. Onomura, J.
Org. Chem. 2009, 74, 9210–9213; g) T. Yamamoto, M.
Iizuka, H. Takenaka, T. Ohta, Y. Ito, J. Organomet.
Chem. 2009, 694, 1325–1332; h) I. N. Francesco, A.
Wagner, F. Colobert, Eur. J. Org. Chem. 2008, 5692–
5695; i) M. Kuriyama, R. Shimazawa, T. Enomoto, R.
Shirai, J. Org. Chem. 2008, 73, 6939–6942; j) M. Kuriya-
ma, R. Shimazawa, R. Shirai, J. Org. Chem. 2008, 73,
1597–1600.
[7] a) M. Kosugi, T. Sumita, K. Ohhashi, H. Sano, T.
Migita, Chem. Lett. 1985, 15, 997–998. The hydroxyme-
thylation of alkenyl halides or its equivalents was ap-
plied to the total syntheses of various natural products,
see selected references: b) K. C. Nicolaou, H. Ding, J.-
A. Richard, D. Y.-K. Chen, J. Am. Chem. Soc. 2010,
132, 3815–3818; c) L. Shen, M. Zhang, Y. Wu, Y. Qin,
Angew. Chem. 2008, 120, 3674–3677; Angew. Chem. Int.
Ed. 2008, 47, 3618–3621; d) D. R. Williams, R. W. Hei-
debrecht Jr, J. Am. Chem. Soc. 2003, 125, 1843–1850;
e) N. Yasuda, D. C. Yang, K. M. Wells, M. S. Jensen,
D. L. Hughes, Tetrahedron Lett. 1999, 40, 427–430.
[13] For selected recent examples with other transition
metal catalysts: a) N. T. S. Phan, T. T. Nguyen, A. H.
Ta, J. Mol. Catal. A 2012, 365, 95–102; b) Y. Yamamo-
to, M. Yohda, T. Shirai, H. Ito, N. Miyaura, Chem.
Asian J. 2012, 7, 2446–2449; c) C. Berinia, O. Navarro,
Chem. Commun. 2012, 48, 1538–1540; d) W. Chen, M.
Baghbanzadeh, C. O. Kappe, Tetrahedron Lett. 2011,
52, 1677–1679; e) Y.-X. Liao, Q.-S. Hu, J. Org. Chem.
2010, 75, 6986–6989; f) J. Karthikeyan, M. Jeganmohan,
C.-H. Cheng, Chem. Eur. J. 2010, 16, 8989–8992; g) C.-
H. Xing, Q.-S. Hu, Tetrahedron Lett. 2010, 51, 924–927;
h) Y. Yamamoto, K. Kurihara, N. Miyaura, Angew.
Chem. 2009, 121, 4478–4480; Angew. Chem. Int. Ed.
2009, 48, 4414–4416; i) H. Zheng, Q. Zhang, J. Chen,
M. Liu, S. Cheng, J. Ding, H. Wu, W. Su, J. Org. Chem.
2009, 74, 943–945; j) T. Zou, S.-S. Pi, J.-H. Li, Org. Lett.
2009, 11, 453–456; k) L. Zhou, X. Du, R. He, Z. Ci, M.
Bao, Tetrahedron Lett. 2009, 50, 406–408; l) S. Mori, M.
Nambo, L.-C. Chi, J. Bouffard, K. Itami, Org. Lett.
2008, 10, 4609–4612; m) A. Yu, B. Cheng, Y. Wu, J. Li,
K. Wei, Tetrahedron Lett. 2008, 49, 5405–5407; n) Y.-X.
Liao, C.-H. Xing, P. He, Q.-S. Hu, Org. Lett. 2008, 10,
2509–2512.
ˇ
[8] a) Z. Hasnꢂk, P. Silhꢃr, M. Hocek, Synlett 2008, 543–
ˇ
546; b) P. Silhꢃr, R. Pohl, I. Votryba, M. Hocek, Org.
Lett. 2004, 6, 3225–3228.
[9] a) N. Murai, M. Yonag, K. Tanaka, Org. Lett. 2012, 14,
1278–1281; b) Eisai R & D Management Co. WO
Patent WO2006/098270A1 2006.
[10] For selected reviews: a) Y.-W. Sun, P.-L. Zhu, Q. Xu,
M. Shi, RSC Adv. 2013, 3, 3153–3168; b) M. Kuriyama,
Chem. Pharm. Bull. 2012, 60, 419–428; c) D. V. Partyka,
Chem. Rev. 2011, 111, 1529–1595.
[11] For selected recent examples with Rh catalysts:
a) A. W. Buesking, J. A. Ellman, Chem. Sci. 2014, 5,
1983–1987; b) C. Zhang, J. Yun, Org. Lett. 2013, 15,
3416–3419; c) D. W. Low, G. Pattison, M. D. Wieczysty,
G. H. Churchill, H. W. Lam, Org. Lett. 2012, 14, 2548–
2551; d) Y.-X. Liao, C.-H. Xing, Q.-S. Hu, Org. Lett.
2012, 14, 1544–1547; e) C.-H. Xing, Y.-X. Liao, P. He,
Q.-S. Hu, Chem. Commun. 2010, 46, 3010–3012; f) J.
Jacq, B. Bessiꢄres, C. Einhorn, J. Einhorn, Org. Biomol.
Chem. 2010, 8, 4927–4933; g) C.-H. Xing, T.-P. Liu,
J. R. Zheng, J. Ng, M. Esposito, Q.-S. Hu, Tetrahedron
Lett. 2009, 50, 4953–4957; h) A. Ros, V. K. Aggarwal,
Angew. Chem. 2009, 121, 6407–6410; Angew. Chem.
Int. Ed. 2009, 48, 6289–6292; i) A. F. Trindade, P. M. P.
Gois, L. F. Veiros, V. Andre, M. T. Duarte, C. A. M.
Afonso, S. Caddick, F. G. N. Cloke, J. Org. Chem. 2008,
73, 4076–4086.
[14] For selected reviews: a) M. N. Hopkinson, C. Richter,
M. Schedler, F. Glorius, Nature 2014, 510, 485–496;
b) T. Drçge, F. Glorius, Angew. Chem. 2010, 122, 7094–
7107; Angew. Chem. Int. Ed. 2010, 49, 6940–6952; c) H.
Clavier, S. P. Nolan, Chem. Commun. 2010, 46, 841–
861; d) W. A. Herrmann, Angew. Chem. 2002, 114,
1342–1363; Angew. Chem. Int. Ed. 2002, 41, 1290–1309;
e) D. Bourissou, O. Guerret, F. P. Gabbaꢅ, G. Bertrand,
Chem. Rev. 2000, 100, 39–92.
[12] For selected recent examples with Pd catalysts: a) M.
Kuriyama, N. Hamaguchi, K. Sakata, O. Onomura, Eur.
J. Org. Chem. 2013, 3378–3385; b) Z. Ye, P. Qian, G.
Lv, F. Luo, J. Cheng, J. Org. Chem. 2010, 75, 6043–
6045; c) R. Zhang, Q. Xu, X. Zhang, T. Zhang, M. Shi,
Tetrahedron: Asymmetry 2010, 21, 1928–1935; d) M.
Kuriyama, N. Ishiyama, R. Shimazawa, O. Onomura,
[15] CCDC 1010975 (5a) and CCDC 1010976 (5d) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
Cambridge
Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[16] L.-C. Campeau, M. Parisien, A. Jean, K. Fagnou, J.
Am. Chem. Soc. 2006, 128, 581–590.
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6 Palladium-Catalyzed Hydroxymethylation of Aryl- and
Heteroarylboronic Acids using Aqueous Formaldehyde
Adv. Synth. Catal. 2014, 356, 1 – 6
Tetsuya Yamamoto,* Azamat Zhumagazin,
Takuma Furusawa, Ryoji Tanaka, Tetsu Yamakawa,*
Yohei Oe, Tetsuo Ohta*
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ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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These are not the final page numbers!