Iridium-Catalyzed, Silyl-Directed, peri-Borylation of C?H Bonds in Fused Polycyclic Arenes and Heteroarenes

Article abstract of DOI:10.1002/anie.201805086

peri-Disubstituted naphthalenes exhibit interesting physical properties and unique chemical reactivity, due to the parallel arrangement of the bonds to the two peri-disposed substituents. Regioselective installation of a functional group at the position peri to 1-substituted naphthalenes is challenging due to the steric interaction between the existing substituent and the position at which the second one would be installed. We report an iridium-catalyzed borylation of the C?H bond peri to a silyl group in naphthalenes and analogous polyaromatic hydrocarbons. The reaction occurs under mild conditions with wide functional group tolerance. The silyl group and the boryl group in the resulting products are precursors to a range of functional groups bound to the naphthalene ring through C?C, C?O, C?N, C?Br and C?Cl bonds.

Full text of DOI:10.1002/anie.201805086

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Accepted Article
Title: Ir-Catalyzed, Silyl-Directed, peri-Borylation of C-H Bonds in
Fused Polycyclic Arenes and Heteroarenes
Authors: Bo Su and John F. Hartwig
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201805086
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http://dx.doi.org/10.1002/ange.201805086

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Bo Su and John F. Hartwig*
Dedication ((optional))
Abstract: peri-Disubstituted naphthalenes exhibit interesting physical
properties and unique chemical reactivity, due to the parallel
arrangement of the bonds to the two peri-disposed substituents.
Regioselective installation of a functional group at the position peri to
1-substituted naphthalenes is challenging due to the steric interaction
between the existing substituent and the position at which the second
one would be installed. We report an iridium-catalyzed borylation of
the C-H bond peri to a silyl group in naphthalenes and analogous
polyaromatic hydrocarbons. The reaction occurs under mild
conditions with wide functional group tolerance. The silyl group and
the boryl group in the resulting products are precursors to a range of
functional groups bound to the naphthalene ring through C-C, C-O, C-
N, C-Br and C-Cl bonds.
the existing substituent and the position at which the second
one would be installed.
Several classical and catalytic methods to peri-substituted
molecules have been studied, but each has severe limitations.
Electrophilic aromatic substitution of 1-substituted
naphthalenes is one approach to synthesize peri-disubstituted
naphthalenes (Scheme 1a), but low yields of the 1,8-
substituted products are obtained because of poor
regioselectivity.[5] Addition of electrophiles to 1,8-
dilithionaphthenes generated by lithium-halogen exchange
and subsequent deprotonation of 1-bromonaphthalenes is a
second approach (Scheme 1a), but this method is limited to
the formation of products containing identical peri-
substituents and limited to reactants containing functional
groups that tolerate organolithium reagents.[6]
peri-Substitution refers to the introduction of a substituent
at the 8 position of 1-substituted naphthalene rings.
Substituents located at mutually peri-positions are much
closer to each other than those at mutually ortho positions.
Due to the rigidity of the backbone of the naphthalene ring
and the juxtaposition of two parallel chemical bonds at the
peri-positions, sterically congested peri-disubstituted
naphthalenes possess special features, including distortions
of the backbone, extreme steric strain, abnormal molecular
spectra, intramolecular hydrogen bonding, high proton
affinity, and unique chemical reactivity.[1] These properties
of peri-disubstituted naphthalenes and related fused arenes
have led to applications of such structures in molecular and
ion recognization,[2] ligand design[3] and catalysis.[2b]
However, the synthesis of these peri-substituted compounds
has been challenging,[4] due to the steric interaction between
Dr. B. Su, Prof. Dr. J. F. Hartwig
Department of Chemistry, University of California Berkeley, CA
94720 (USA)
E-mail: jhartwig@berkeley.edu
((Please delete this text if not appropriate))
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Scheme 1. Functionalization at the peri-positions of naphthalene and related
compounds
entries
1-5).
Reactions
with
3,4,7,8-tetramethyl
phenanthroline L5 formed product 2a in higher yield (61%)
than those with 4,4’-di-tert-butyl bipyridine L1 and
phenanthroline ligands L2-L4 (up to 47%). Reactions
conducted in alternative solvents and at higher temperatures
did not occur in higher yield (Table 1, entries 6-12), but
reactions with 1.5 equiv of B2pin2 instead of 1.2 equiv
occurred in a higher 68% yield. Ultimately, the product was
obtained in a high 84% when the reaction was run with 1.5
equiv of B2pin2 for a longer 24 h.
The functionalization of C-H bonds catalyzed by transition
metal-complexes is a third approach.[7] In specific cases, this
type of reaction can install a substituent peri to an OH or NH2
group of naphthols and naphthylamines. However, the
reactions of naphthols at the peri position have been limited
to phenylation at high temperatures and a series of
alkynylations,[7a, 7n] while the reactions of naphthylamines at
the peri position have required picolinamide as the directing
group and lead to the installation of a limited set of groups.[7b,
Table 1: Evaluation of the silyl-directed borylation of the peri-C-H bond.[a]
7d, 7g-i, 7k-m]
In other cases, reactions of 1-naphthol and 1-
aminonaphthalene derivatives have formed annulated
products in which the directing groups (OH and NR) are
linked to the newly installed functionalities (Scheme 1b).[7c-f,
7k, 7o, 8]
In such structures, manipulations of the directing
group and the newly introduced functional groups is difficult.
Other directing groups (eg. carbolic acid, amide, 2-pyridyl
group etc.) have led to ortho-substituted products,[7n, 9] rather
than peri-substituted products.
The borylation of aromatic C-H bonds catalyzed by
transition-metal catalysts usually occurs under mild
conditions with high functional group compatibility, and the
C-B bond in the product undergoes a wide range of
transformations.[10], [11] Due to steric hindrance between peri-
positions, no undirected C-H borylation has occurred at the
peri-positions of naphthalenes. All of the catalytic, directed
borylation of C-H bonds in 1-substituted naphthalenes,
including those containing 1-quinolyl-, 2-pyridyl, ester,
amide or carbamate moieties, have occurred at the position
ortho, not the peri, to the directing groups (Scheme 1c).[11e,
11h, 11j, 11k, 11n]
Thus, a strategy to enable the installation of a
series of substituents at mutually peri positions for the
synthesis of a wide range of peri-substituted polycylic
aromatic hydrocarbons is needed.
[a]The reaction was conducted with 1a (0.20 mmol), [Ir(cod)OMe]2
(2.0 mol %), ligand (4.5 mol %), and B2pin2 (1.2 equiv) in the solvent
(1.0 mL) for 12 h under N2. [b]The yield was determined by 1H NMR spectrum
using CH2Br2 as internal standard. [c]The reaction was conducted with 1.5
equiv. of B2pin2. [d]The reaction was conducted for 24 h.
Our group has reported silyl-directed borylations of C-H
bonds, in which the borylation occurred at ortho-position of
aromatic C-H bonds or C(sp3)-H bonds.[12], [13] The silyl group
adds transiently to the metal center and can be used after the
borylation reaction to create a range of functional groups by
transformations that are orthogonal in most cases to those of
the transformations of C-B bonds, thus largely increasing the
product diversity.[12]
Having identified conditions for the silyl-directed, peri-
borylation of compound 1a, we assessed the scope of the
reaction
(Table
2).
Reactions
of
1-
dimethylhydrosilylnaphthalenes containing a range of
functional groups afforded the products from borylation of
the peri-C-H bonds in moderate to good yields. To test the
tolerance of this reaction for functional groups, the
borylation was conducted with a series of 1-hydrosilyl-4-
substituted naphthalenes. Unsubstituted 1a and alkyl- or
aryl-substituted 1b and 1c gave the products 2a-2c in 54%-
82% yields. Reactions of the naphthalenes containing
fluoride or bromide (2d and 2e), a trimethylsilyl group
(2f), a silyl ether (2g), a pivalate ester (2h), a carbonate
(2i), a carbamate (2j), a methyl sulfonate (2k) and even a
labile ketal (2l) gave the peri-substituted product in 47-
72% yields.
We report the peri borylation of C-H bonds in 1-hydrosilyl
naphthalenes and related polyaromatic hydrocarbons
(Scheme 1d). This reaction occurs under mild conditions with
high functional group compatibility. Reactions at the C-Si
and C-B bonds in the peri-borylated arenes form final
products containing a range of substituents bound to the arene
unit by C-C, C-O, C-N, C-Cl and C-Br bonds.
To identify conditions for the Ir-catalyzed, peri borylation
of C-H bonds in 1-hydrosilyl naphthalenes, we conducted
reactions of 1-dimethylhydrosilyl naphthalene 1a with B2pin2
catalyzed by iridium complexes derived from [Ir(cod)OMe]2
o
and N, N-donor ligands L1-L5 in THF at 80 C (Table 1,
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Reactions of substrates containing varied electronic and
steric properties of the arenes were also conducted.
Substituents located para to the silyl group with varied
electronic properties did not affect the yield (2m-2o).
Moreover, reactions of 3-substituted, 5-substituted, and 6-
substituted 1-silyl naphthalenes 1p-1s underwent
borylation at the peri-C-H bond smoothly to give products
2p-2s in good yields. However, the reaction of 2-methoxy-
substituted 1t did not give any product from borylation,
presumably because the steric demand of a 2-substituent
causes the silyl group to adopt a conformation in which the
Si-H bond is more hindered because it is oriented toward
the 2-substituent, rather than the peri-C-H bond.
phenanthrene 3c, 3-hydrosilyl perylene 3d, 1-hydrosilyl
pyrene 3e and 1-hydrosilyl chrysene 3f formed the
corresponding peri-borylated products 4c-4f in moderate to
good yields. Moreover, reactions occurred with the
heteroaromatic 1-substituted isoquinolines 3g-3h to give the
corresponding peri-substituted products 4g-4h. For reasons
we do not understand, no reaction occurred when 2-chloro-4-
hydrosilyl quinoline and 1-phenylsulfonyl-3-hydrosilyl
indole (structures not shown) were subjected to the reaction
conditions.
Table 3: Scope of the silyl-directed peri-C-H borylation of isoquinolines and
other polyaromatics hydrocarbons.[a]
Table 2: Scope of the silyl-directed peri-C-H borylation of naphthalenes.[a]
[a]The reaction was conducted under N2 for 18-24 h and was
monitored by GC/MS; the yields refer to isolated yields.
This silyl-directed peri-selective C-H borylation occurred
on a gram scale in yields similar to the reactions on smaller
scale. The reaction of 1a with 6.0 mmol of silylarene (1.1 g)
(eq 1) formed the borylated product 2a in 74% yield with only
0.50 mol % catalyst, instead of the 2.0 mol % catalyst used
for reactions with 0.20 mmol of the silylarene.
[a]The reaction was conducted under N2 for 18-24 h and was
monitored by GC/MS; the yields refer to isolated yields.
This silyl-directed peri-borylation of C-H bonds also
occurred with polyaromatic hydrocarbons (PAHs) and
benzo-fused heteroaromatic compounds (Table 3). These
compounds are commonly used in material chemistry,[14] and
selective functionalization of these compounds by alternative
methods is challenging because they contain a large set of
distinct aromatic C-H bonds.[15] However, the silyl-directed
borylation occurred selectively at the C-H bonds located peri
to the silyl group in 5-hydrosilyl acenaphthene 3a and 4-
hydrosilyl-7,7-dimethyl-7H-benzo[de]anthracene 3b to form
the corresponding products 4a and 4b in 75% and 54% yields.
The reactions with additional PAHs, such as 1-hydrosilyl
To illustrate the utility of this reaction, we investigated
transformations of the boryl and the silyl groups in compound
2a. Boronate 2a was transformed to peri silyl boronic
anhydride 5 in the presence of a ruthenium catalyst.
Compound 5 was presumably formed via oxidation of the
silane to the corresponding silanols, followed by
displacement of the pinacol by intramolecular substitution
and hydrolysis.[16] The C-B bond in 5 was converted to a C-
C bond in a biaryl by a palladium-catalyzed Suzuki-coupling
reaction.[17] The C-B bond in 5 also was transformed to a C-
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halogen bond (C-Br and C-Cl) and C-N bond by copper-
catalyzed and copper-mediated processes.[18] The C-B bond
in 5 also was oxidized selectively to a C-O bond, while
leaving the C-Si bond intact, with 1.5 equiv of m-CPBA as
the oxidant to form the naphthalene-fused silole 10 after
dehydration. Oxidation of both the C-B and C-Si bonds in 5
occurred to give naphthalene-1,8-diol when an excess of
H2O2 was used under basic conditions.
tolerance. Both the boryl group and the silyl group at the
peri-positions have been transformed to a wide range of
groups, such as aryl groups, hydroxyl groups, an azido
group and halogens. This reaction greatly expands the
diversity of readily accessible peri-disubstituted
naphthalenes and related polyaromatic hydrocarbons, and
further studies will be conducted to expand the scope of
peri-selective reactions of fused heteroarenes.
Acknowledgements ((optional))
We thank the NIH (GM-115812) for support.
.
Keywords: C-H activation • peri selective • peri-disubstitued •
borylation • naphthalene •
References
[1]
[2]
V. Balasubramaniyan, Chem. Rev. 1966, 66, 567-641.
a) H. A. Staab, T. Saupe, Angew. Chem. Int. Ed. 1988, 27, 865-879; b)
F. P. Schmidtchen, M. Berger, Chem. Rev. 1997, 97, 1609-1646; c) L.
Sobczyk, J. Mol. Struct. 2010, 972, 59-63; d) A. F. Pozharskii, V. A.
Ozeryanskii, Mendeleev Commun. 2012, 22, 117-124.
Scheme 2. Transformations of the C-B bond in the borylated product
[3]
̈
a) J. D. Hoefelmeyer, M. Schulte, M. Tschinkl, F. P. Gabbaı, Coord.
Chem. Rev. 2002, 235, 93-103; b) P. Kilian, F. R. Knight, J. D. Woollins,
Coord. Chem. Rev. 2011, 255, 1387-1413; c) P. Kilian, F. R. Knight, J.
D. Woollins, Chem. Eur. J. 2011, 17, 2302-2328.
To expand the diversity of the products derived from the
peri-C-H borylation further, transformations of the C-Si
bond in 6 were explored. The C-Si bond in compound 6
was oxidized to the C-O bond in naphthol 12 when treated
with a combination of hydrogen peroxide, base and
fluoride. Halogenation of the C-Si bond in 6 with NXS (X
= Br and Cl) and AgF occurred smoothly to give products
13 and 14 in 71% and 65% yields respectively.[19] The C-
Si bond also was converted to a C-C bond in the 1,8-
diarylnaphthalene by palladium-catalyzed coupling.[20]
[4]
[5]
[6]
G. Booth, in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH
Verlag GmbH & Co. KGaA, 2000.
A. Daştan, M. Nawaz Tahir, D. Ülkü, M. Balci, Tetrahedron 1999, 55,
12853-12864.
a) H. E. Katz, J. Org. Chem. 1985, 50, 5027-5032; b) J. v. Soolingen, R.
J. De Lang, R. d. Besten, P. A. A. Klusener, N. Veldman, A. L. Spek, L.
Brandsma, Synth. Commun. 1995, 25, 1741-1744.
[7]
a) T. Satoh, Y. Kawamura, M. Miura, M. Nomura, Angew. Chem. Int. Ed.
1997, 36, 1740-1742; b) Y. Nishinaka, T. Satoh, M. Miura, H. Morisaka,
M. Nomura, H. Matsui, C. Yamaguchi, Bull. Chem. Soc. Jpn. 2001, 74,
1727-1735; c) S. Mochida, M. Shimizu, K. Hirano, T. Satoh, M. Miura,
Chem. Asian J. 2010, 5, 847-851; d) X. Li, X. Gong, M. Zhao, G. Song,
J. Deng, X. Li, Org. Lett. 2011, 13, 5808-5811; e) X. Tan, B. Liu, X. Li, B.
Li, S. Xu, H. Song, B. Wang, J. Am. Chem. Soc. 2012, 134, 16163-16166;
f) V. S. Thirunavukkarasu, M. Donati, L. Ackermann, Org. Lett. 2012, 14,
3416-3419; g) L. Grigorjeva, O. Daugulis, Angew. Chem. Int. Ed. 2014,
53, 10209-10212; h) L. Huang, X. Sun, Q. Li, C. Qi, J. Org. Chem. 2014,
79, 6720-6725; i) M. Iwasaki, W. Kaneshika, Y. Tsuchiya, K. Nakajima,
Y. Nishihara, J. Org. Chem. 2014, 79, 11330-11338; j) J. Karthikeyan, N.
Yoshikai, Org. Lett. 2014, 16, 4224-4227; k) X. Zhang, W. Si, M. Bao, N.
Asao, Y. Yamamoto, T. Jin, Org. Lett. 2014, 16, 4830-4833; l) Z. Li, S.
Sun, H. Qiao, F. Yang, Y. Zhu, J. Kang, Y. Wu, Y. Wu, Org. Lett. 2016,
18, 4594-4597; m) L. Wang, M. Yang, X. Liu, H. Song, L. Han, W. Chu,
Z. Sun, Appl. Organomet. Chem. 2016, 30, 680-683; n) E. Tan, A. I.
Konovalov, G. A. Fernández, R. Dorel, A. M. Echavarren, Org. Lett. 2017,
19, 5561-5564; o) Y. Tokoro, T. Oyama, Chem. Lett. 2018, 47, 130-133.
a) F. Wang, G. Song, Z. Du, X. Li, J. Org. Chem. 2011, 76, 2926-2932;
b) J. Jayakumar, K. Parthasarathy, Y.-H. Chen, T.-H. Lee, S.-C. Chuang,
C.-H. Cheng, Angew. Chem. Int. Ed. 2014, 53, 9889-9892; c) R. Shi, L.
Lu, H. Xie, J. Yan, T. Xu, H. Zhang, X. Qi, Y. Lan, A. Lei, Chem. Commun.
2016, 52, 13307-13310.
Scheme 3. Further transformations of the C-Si bond in the product
In summary, we have developed an iridium-catalyzed,
peri borylation of naphthalene derivatives and analogous
polyaromatic hydrocarbons directed by a hydrosilyl group
under mild conditions with broad functional-group
[8]
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[9]
a) O. Daugulis, V. G. Zaitsev, Angew. Chem. Int. Ed. 2005, 44, 4046-
4048; b) J. Wencel-Delord, C. Nimphius, H. Wang, F. Glorius, Angew.
Chem. Int. Ed. 2012, 51, 13001-13005; c) M. Iwasaki, M. Iyanaga, Y.
Tsuchiya, Y. Nishimura, W. Li, Z. Li, Y. Nishihara, Chem. Eur. J. 2014,
20, 2459-2462.
[10] a) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig,
Chem. Rev. 2010, 110, 890-931; b) A. Ros, R. Fernandez, J. M.
Lassaletta, Chem. Soc. Rev. 2014, 43, 3229-3243; c) L. Xu, S. Zhang, P.
Li, Chem. Soc. Rev. 2015, 44, 8848-8858.
[11] a) S. Kawamorita, H. Ohmiya, K. Hara, A. Fukuoka, M. Sawamura, J. Am.
Chem. Soc. 2009, 131, 5058-5059; b) T. Ishiyama, H. Isou, T. Kikuchi,
N. Miyaura, Chem. Commun. 2010, 46, 159-161; c) H.-X. Dai, J.-Q. Yu,
J. Am. Chem. Soc. 2011, 134, 134-137; d) S. Kawamorita, T. Miyazaki,
H. Ohmiya, T. Iwai, M. Sawamura, J. Am. Chem. Soc. 2011, 133, 19310-
19313; e) A. Ros, B. Estepa, R. López-Rodríguez, E. Álvarez, R.
Fernández, J. M. Lassaletta, Angew. Chem. Int. Ed. 2011, 50, 11724-
11728; f) A. J. Roering, L. V. A. Hale, P. A. Squier, M. A. Ringgold, E. R.
Wiederspan, T. B. Clark, Org. Lett. 2012, 14, 3558-3561; g) P. C. Roosen,
V. A. Kallepalli, B. Chattopadhyay, D. A. Singleton, R. E. Maleczka, M.
R. Smith, J. Am. Chem. Soc. 2012, 134, 11350-11353; h) Y. Kuninobu,
T. Iwanaga, T. Omura, K. Takai, Angew. Chem. Int. Ed. 2013, 125, 4527-
4530; i) K. M. Crawford, T. R. Ramseyer, C. J. A. Daley, T. B. Clark,
Angew. Chem. Int. Ed. 2014, 53, 7589-7593; j) J. A. Fernandez-Salas, S.
Manzini, L. Piola, A. M. Z. Slawin, S. P. Nolan, Chem. Commun. 2014,
50, 6782-6784; k) B. Ghaffari, S. M. Preshlock, D. L. Plattner, R. J.
Staples, P. E. Maligres, S. W. Krska, R. E. Maleczka, M. R. Smith, J. Am.
Chem. Soc. 2014, 136, 14345-14348; l) Y. Kuninobu, H. Ida, M. Nishi, M.
Kanai, Nat. Chem. 2015, 7, 712-717; m) R. Bisht, B. Chattopadhyay, J.
Am. Chem. Soc. 2016, 138, 84-87; n) G. Wang, L. Liu, H. Wang, Y.-S.
Ding, J. Zhou, S. Mao, P. Li, J. Am. Chem. Soc. 2016, 139, 91-94; o) H.
L. Li, Y. Kuninobu, M. Kanai, Angew. Chem. Int. Ed. 2017, 56, 1495-1499.
[12] a) T. A. Boebel, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130, 7534-7535;
b) D. W. Robbins, T. A. Boebel, J. F. Hartwig, J. Am. Chem. Soc. 2010,
132, 4068-4069; c) S. H. Cho, J. F. Hartwig, J. Am. Chem. Soc. 2013,
135, 8157-8160; d) S. H. Cho, J. F. Hartwig, Chem. Sci. 2014, 5, 694-
698; e) M. A. Larsen, S. H. Cho, J. Hartwig, J. Am. Chem. Soc. 2016,
138, 762-765.
[13] a) S. Bracegirdle, E. A. Anderson, Chem. Soc. Rev. 2010, 39, 4114-
4129; b) M. Parasram, V. Gevorgyan, Acc. Chem. Res. 2017, 50, 2038-
2053.
[14] a) C. Former, S. Becker, A. C. Grimsdale, K. Müllen, Macromolecules
2002, 35, 1576-1582; b) B. A. Jones, M. J. Ahrens, M.-H. Yoon, A.
Facchetti, T. J. Marks, M. R. Wasielewski, Angew. Chem. Int. Ed. 2004,
43, 6363-6366; c) S. Bhosale, A. L. Sisson, P. Talukdar, A. Fürstenberg,
N. Banerji, E. Vauthey, G. Bollot, J. Mareda, C. Röger, F. Würthner, N.
Sakai, S. Matile, Science 2006, 313, 84-86; d) X. Zhang, S. Rehm, M. M.
Safont-Sempere, F. Würthner, Nat. Chem. 2009, 1, 623; e) X. Zhan, A.
Facchetti, S. Barlow, T. J. Marks, M. A. Ratner, M. R. Wasielewski, S. R.
Marder, Adv. Mater. 2011, 23, 268-284.
[15] a) D. N. Coventry, A. S. Batsanov, A. E. Goeta, J. A. K. Howard, T. B.
Marder, R. N. Perutz, Chem. Commun. 2005, 2172-2174; b) Y.
Avlasevich, C. Li, K. Mullen, J. Mater. Chem. 2010, 20, 3814-3826; c) Y.
Zagranyarski, L. Chen, D. Jänsch, T. Gessner, C. Li, K. Müllen, Org. Lett.
2014, 16, 2814-2817.
[16] B. Chatterjee, C. Gunanathan, Chem. Commun. 2017, 53, 2515-2518.
[17] S. Lavieri, J. A. Zoltewicz, J. Org. Chem. 2001, 66, 7227-7230.
[18] a) H. Yang, Y. Li, M. Jiang, J. Wang, H. Fu, Chem. Eur. J. 2011, 17,
5652-5660; b) B. Su, T.-G. Zhou, P.-L. Xu, Z.-J. Shi, J. F. Hartwig, Angew.
Chem. Int. Ed. 2017, 56, 7205-7208; c) A. Winter, A. Wild, R.
Hoogenboom, M. W. M. Fijten, M. D. Hager, R.-A. Fallahpour, U. S.
Schubert, Synthesis 2009, 2009, 1506-1512; d) S. Yoshida, K.
Shimomori, T. Nonaka, T. Hosoya, Chem. Lett. 2015, 44, 1324-1326.
[19] B. Su, J. F. Hartwig, J. Am. Chem. Soc. 2017, 139, 12137-12140.
[20] S. Akai, T. Ikawa, S. i. Takayanagi, Y. Morikawa, S. Mohri, M.
Tsubakiyama, M. Egi, Y. Wada, Y. Kita, Angew. Chem. Int. Ed. 2008, 47,
7673-7676.
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Layout 2:
COMMUNICATION
Bo Su and John F. Hartwig*
Page No. – Page No.
Ir-Catalyzed, Silyl-Directed, peri-
Borylation of C-H Bonds in Fused
Polycyclic Arenes and Heteroarenes
Peri-Functionalization via C-H Borylation: An iridium-catalyzed, hydrosilyl directed, peri-C-H
borylation of naphthalenes and analogous polyaromatic hydrocarbons has been developed. The reaction
occurs under mild conditions with broad functional-group tolerance. Both the boryl group and the silyl
group at the peri-positions can be transformed to a wide range of groups, such as aryl groups, hydroxyl
groups, an azido group and halogens. This reaction greatly expands the diversity of readily accessible
peri-disubstituted naphthalenes and related polyaromatic hydrocarbons.
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