Nucleophilicity of a base-stabilized borole anion at the boron center

Article abstract of DOI:10.1002/anie.201000386

(Chemical Equation Presented) A piece of the π: A nucleophilic carbenestabilized boryl anion has been prepared by reduction (see scheme). Reactions of this boracycle indicated its nucleophilicity on a π orbital of the central boron atom. The significance of this work is presented along with a background on nucleophilic boron reagents and boracycles.

Full text of DOI:10.1002/anie.201000386

Highlights
DOI: 10.1002/anie.201000386
Nucleophilic Boron
Nucleophilicity of a Base-Stabilized Borole Anion at the
Boron Center
Makoto Yamashita*
boron · carbenes · heterocycles · nucleophilicity ·
reduction
N
eutral boron-containing compounds are widely used in
ophilicity on the boron center to react with organic and
inorganic electrophiles.
organic and inorganic molecular chemistry. Most of these
species have Lewis acidity because of a vacant p orbital that
accepts a lone pair from a Lewis base. The highly acidic nature
of the boron atom has limited syn-
Boroles, which are isoelectronic to the cyclopentadienyl
(Cp) cation and have 4p electrons that form an antiaromatic
system, can generally accept two electrons into a vacant
p orbital of the boron center to generate the corresponding
stable 6p electron system E with two negative charges
(Scheme 2a). This aromatic and dianionic nature have led
thetic methodologies to produce bor-
on-containing materials. Therefore,
development of nucleophilic boron
reagents has been considered as one
of the most important issues in boron
chemistry. In this context, four types
of nucleophilic boron reagents have been reported in the last
two decades (Scheme 1). The first report of Lewis base
stabilized dihydroboryl anion A described a number of
Scheme 2. Reduction of boron-substituted boroles and Lewis base
stabilized boroles (substituents on carbon atoms are omitted for
clarity). LB=Lewis base.
Scheme 1. Examples of nucleophilic boron reagents.
reactions with various electrophiles to give the corresponding
substituted products and adducts, although the reagent itself
was not structurally characterized.[1] The discovery of bor-
ylcopper species B, prepared from copper salts and bis(pina-
colato)diborane(4) by two independent groups, namely Ito
and Hosomi[2] and Ishiyama and Miyaura,[3] resulted in a rapid
expansion of the chemistry of nucleophilic borylcopper
reagents to applications in a variety of organic syntheses.[4]
A simple boryl anion, boryl lithium (C),[5] appeared on 2006
and showed its strong anionic nature, with nucleophilicity
towards many electrophiles and transmetallation ability to
form the corresponding boryl metal species. Recent research
on transition metal borylene complexes[6] also gave a unique
and anionic dimetalloborylene species (D)[7] having a nucle-
to E being applied to organotransition metal chemistry as a
dianion analogue of the Cp ligand.[8] It can be expected that
the similar reduction of a neutral and Lewis base stabilized
borole, which has one electron in its p orbital because of a
coordination bond from the Lewis base to the sp2 orbital of
the boron center, may give the corresponding monoanionic
Lewis base-stabilized borole derivative F (Scheme 2b).
However, this type of compound has not been synthesized
and isolated to date.
It has been shown that N-heterocyclic carbenes (NHC),
which are singlet carbenes stabilized with adjacent nitrogen
atom(s), were effective in stabilizing electron-deficient boron
compounds, such as diborene,[9] the borenium cation,[10] and 9-
boraanthracene[11] (Scheme 3). Based on the high donor
ability of NHC, it can be expected that the above-mentioned
Lewis base-stabilized borole anion could be synthesized by
use of NHC.
[*] Dr. M. Yamashita
Department of Chemistry and Biotechnology
Graduate School of Engineering
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, 113-8656 Tokyo (Japan)
Fax : (+81)3-5841-7263
Braunschweig et al. now report a synthesis of NHC-
stabilized B-chloropentaphenylborole 1[12] based on their
previous report for a synthesis of Lewis base stabilized borole
derivatives (Scheme 4).[13] Upon reduction of 1 with an excess
amount of KC8 in diethyl ether, they isolated the correspond-
E-mail: makotoy@chembio.t.u-tokyo.ac.jp
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ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2010, 49, 2474 – 2475

Angewandte
Chemie
[1] a) A. Blumenthal, P. Bissinger, H. Schmidbaur, J. Organomet.
Chem. 1993, 462, 107; b) T. Imamoto, T. Hikosaka, J. Org. Chem.
1994, 59, 6753.
[2] H. Ito, H. Yamanaka, J. Tateiwa, A. Hosomi, Tetrahedron Lett.
2000, 41, 6821.
[3] K. Takahashi, T. Ishiyama, N. Miyaura, Chem. Lett. 2000, 29, 982.
[4] L. Dang, Z. Lin, T. B. Marder, Chem. Commun. 2009, 3987.
[5] a) Y. Segawa, M. Yamashita, K. Nozaki, Science 2006, 314, 113;
b) Y. Segawa, M. Yamashita, K. Nozaki, Angew. Chem. 2007,
119, 6830; Angew. Chem. Int. Ed. 2007, 46, 6710; c) M.
Yamashita, Y. Suzuki, Y. Segawa, K. Nozaki, J. Am. Chem.
Soc. 2007, 129, 9570; d) T. Kajiwara, T. Terabayashi, M.
Yamashita, K. Nozaki, Angew. Chem. 2008, 120, 6708; Angew.
Chem. Int. Ed. 2008, 47, 6606; e) Y. Segawa, Y. Suzuki, M.
Yamashita, K. Nozaki, J. Am. Chem. Soc. 2008, 130, 16069; f) M.
Yamashita, Y. Suzuki, Y. Segawa, K. Nozaki, Chem. Lett. 2008,
37, 802; g) T. Terabayashi, T. Kajiwara, M. Yamashita, K.
Nozaki, J. Am. Chem. Soc. 2009, 131, 14162.
Scheme 3. NHC-stabilized boron compounds. Ar=Dip (2,6-
(iPr)2C6H3), Mes (2,4,6-Me3C6H2).
Scheme 4. Synthesis of NHC-stabilized borole anion 2 by reduction
with KC8 and its reaction with methyl iodide.
[6] a) H. Braunschweig, Angew. Chem. 1998, 110, 1882; Angew.
Chem. Int. Ed. 1998, 37, 1786; b) H. Braunschweig, M. Colling,
Coord. Chem. Rev. 2001, 223, 1; c) H. Braunschweig, M. Colling,
Eur. J. Inorg. Chem. 2003, 393; d) H. Braunschweig, Adv.
Organomet. Chem. 2004, 51, 163; e) H. Braunschweig, G. R.
Whittell, Chem. Eur. J. 2005, 11, 6128; f) H. Braunschweig, C.
Kollann, D. Rais, Angew. Chem. 2006, 118, 5380; Angew. Chem.
Int. Ed. 2006, 45, 5254; g) H. Braunschweig, C. Kollann, F.
Seeler, Struct. Bonding (Berlin) 2008, 130, 1; h) S. Aldridge, D. L.
Coombs, Coord. Chem. Rev. 2004, 248, 535; i) D. Vidovic, G. A.
Pierce, S. Aldridge, Chem. Commun. 2009, 1157.
ing monoanionic compound 2, which can be regarded as an
isoelectronic species to the cyclopentadienyl anion. The
11B NMR signal of 2 appeared at dB = 12 ppm, which is
shifted remarkably upfield compared to those of borata-
alkenes or borole dianions.
The solid-state structure of 2 was unambiguously deter-
mined by X-ray crystallography. The potassium cation sit on
the borole ring with simultaneous coordination from a phenyl
À
[7] a) H. Braunschweig, M. Burzler, R. D. Dewhurst, K. Radacki,
Angew. Chem. 2008, 120, 5732; Angew. Chem. Int. Ed. 2008, 47,
5650; b) H. Braunschweig, P. Brenner, R. D. Dewhurst, M.
Kaupp, R. Mꢁller, S. ꢂstreicher, Angew. Chem. 2009, 121, 9916;
Angew. Chem. Int. Ed. 2009, 48, 9735.
ring of the second molecule to construct a dimer. A short B
Ccarbene bond (1.5406(15) ꢀ), a small dihedral angle between
boron and carbene planes (36.38), and DFT calculations on a
model compound indicated a significant p back-donation
from an anionic boron center to the carbene carbon in 2.
Surprisingly, the NHC-stabilized borole anion 2 reacts
with methyl iodide at boron to form the substituted product 3
with an sp3-hybridized boron atom; the product was isolated
in 71% yield (Scheme 4). The highly nucleophilic nature of
the anionic p orbital on the boron center is very unique,
because the similar boron compounds, namely borabenzene,
boratabenzene, and borataalkene, have a boron-containing
conjugate p-system with no nucleophilicity at boron. The
nucleophilicity is consistent with DFT calculations, which
showed a contribution to the HOMO from the boron center.
This outstanding advance in molecular boron chemistry
affords a new concept, with nucleophilicity on the p orbital of
the boron center allowing the design of boron-containing
functional materials. There is also a plenty of room for an
application of the base-stabilized borole anion to transition
metal chemistry as a designable alternative to the Cp ligand,
because many NHCs are now available having a variety of
steric and electronic effects, functional groups on their side
chain, and chiral centers.[14]
[8] a) D. Loginov, D. Muratov, A. Kudinov, Russ. Chem. Bull. 2008,
57, 1; b) I. Hyla-Kryspin, R. Gleiter, G. E. Herberich, M.
Benard, Organometallics 1994, 13, 1795; c) R. Gleiter, I. Hyla-
Kryspin, G. E. Herberich, J. Organomet. Chem. 1994, 478, 95;
d) G. J. Pindado, S. J. Lancaster, M. Thornton-Pett, M. Boch-
mann, J. Am. Chem. Soc. 1998, 120, 6816; e) C. K. Sperry, G. C.
Bazan, W. D. Cotter, J. Am. Chem. Soc. 1999, 121, 1513.
[9] a) Y. Wang, B. Quillian, P. Wei, C. S. Wannere, Y. Xie, R. B.
King, H. F. Schaefer, P. von R. Schleyer, G. H. Robinson, J. Am.
Chem. Soc. 2007, 129, 12412; b) Y. Wang, B. Quillian, P. Wei, Y.
Xie, C. S. Wannere, R. B. King, H. F. Schaefer, P. von R.
Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2008, 130, 3298.
[10] T. Matsumoto, F. P. Gabbaꢃ, Organometallics 2009, 28, 4252.
[11] T. K. Wood, W. E. Piers, B. A. Keay, M. Parvez, Angew. Chem.
2009, 121, 4069; Angew. Chem. Int. Ed. 2009, 48, 4009.
[12] H. Braunschweig, C.-W. Chiu, K. Radacki, T. Kupfer, Angew.
Chem. 2010, 122, 2085; Angew. Chem. Int. Ed. 2010, 49, 2041.
[13] H. Braunschweig, T. Kupfer, Chem. Commun. 2008, 4487.
[14] a) S. T. Liddle, I. S. Edworthy, P. L. Arnold, Chem. Soc. Rev.
2007, 36, 1732; b) P. L. Arnold, I. J. Casely, Chem. Rev. 2009, 109,
3599; c) N. Marion, S. Dꢄez-Gonzꢅlez, S. P. Nolan, Angew. Chem.
2007, 119, 3046; Angew. Chem. Int. Ed. 2007, 46, 2988; d) P.
de Frꢆmont, N. Marion, S. P. Nolan, Coord. Chem. Rev. 2009,
253, 862; e) S. Dꢄez-Gonzꢅlez, N. Marion, S. P. Nolan, Chem.
Rev. 2009, 109, 3612; f) N-Heterocyclic Carbenes in Synthesis
(Ed.: S. P. Nolan), Wiley-VCH, Wiley, 2006.
Received: January 22, 2010
Published online: March 5, 2010
Angew. Chem. Int. Ed. 2010, 49, 2474 – 2475
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
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