Chemical Science
Edge Article
borole products. An attempt to access an eight-membered ring
was unsuccessful with 1,1-diphenylethylene oxide, instead
forging a new BOC3 ring that is a component in effective
pharmacophores. The reactions all required heat to crack the
6 (a) F. J ¨a kle, Chem. Rev., 2010, 110, 3985–4022; (b) E. Von
Grotthuss, A. John, T. Kaese and M. Wagner, Asian J. Org.
Chem., 2018, 7, 37–53; (c) A. Lorbach, A. Hubner and
M. Wagner, Dalton Trans., 2012, 41, 6048–6063; (d)
C. D. Entwistle and T. B. Marder, Angew. Chem., Int. Ed.,
2002, 41, 2927–2931; (e) D. Frath, J. Massue, G. Ulrich and
R. Ziessel, Angew. Chem., Int. Ed., 2014, 53, 2290–2310; (f)
D. T. Yang, S. K. Mellerup, J. B. Peng, X. Wang, Q. S. Li and
S. N. Wang, J. Am. Chem. Soc., 2016, 138, 11513–11516; (g)
F. Vidal and F. J ¨a kle, Angew. Chem., Int. Ed., 2019, 58, 5846–
5870; (h) F. J ¨a kle, Coord. Chem. Rev., 2006, 250, 1107–1121.
7 (a) Z. F. Xi, Acc. Chem. Res., 2010, 43, 1342–1351; (b) Z. Zhang,
R. M. Edkins, M. Haehnel, M. Wehner, A. Eichhorn,
L. Mail ¨a nder, M. Meier, J. Brand, F. Brede, K. M u¨ ller-
Buschbaum, H. Braunschweig and T. B. Marder, Chem.
Sci., 2015, 6, 5922–5927; (c) T. Heitkemper and
C. P. Sindlinger, Chem.–Eur. J., 2019, 25, 6628–6637.
ꢀ
dimer but were all complete within 24 h at 100 C. Dimers with
different substitution on boron and carbon are also capable of
insertion reactions, exemplied in the reactions with diphe-
nylketene. These studies solidify that bottleable monomeric
boroles are not essential for insertion chemistry and that
dimers have great potential to act as borole synthons to furnish
a
wealth of heterocycles with less restrictions on the
substitution.
Conflicts of interest
There are no conicts to declare.
8
(a) G. E. Herberich, B. Buller, B. Hessner and W. Oschmann,
J. Organomet. Chem., 1980, 195, 253–259; (b) X. Y. Yan and
C. J. Xi, Acc. Chem. Res., 2015, 48, 935–946.
Acknowledgements
We are grateful to the Welch Foundation (Grant No. AA-1846) and
the National Science Foundation for a CAREER Award (Award No.
9
(a) S. Yruegas, C. Wilson, J. L. Dutton and C. D. Martin,
Organometallics, 2017, 36, 2581–2587; (b) H. Braunschweig,
F. Hupp, I. Krummenacher, L. Mail ¨a nder and F. Rauch,
Chem.–Eur. J., 2015, 21, 17844–17849; (c) A. Fukazawa,
J. L. Dutton, C. Fan, L. G. Mercier, A. Y. Houghton, Q. Wu,
W. E. Piers and M. Parvez, Chem. Sci., 2012, 3, 1814–1818;
1753025) for their generous support of this work. We thank John
R. Tidwell for assistance in X-ray diffraction analysis.
Notes and references
(
d) K. Huang, S. A. Couchman, D. J. Wilson, J. L. Dutton
1
J. J. Eisch, N. K. Hota and S. Kozima, J. Am. Chem. Soc., 1969,
1, 4575–4577.
(a) H. Braunschweig and T. Kupfer, Chem. Commun., 2011,
7, 10903–10914; (b) H. Braunschweig, I. Fern ´a ndez,
and C. D. Martin, Inorg. Chem., 2015, 54, 8957–8968; (e)
K. Huang and C. D. Martin, Inorg. Chem., 2015, 54, 1869–
1875; (f) Y. T. Su and R. Kinjo, Chem. Soc. Rev., 2019, 48,
3613–3659.
9
2
4
G. Frenking and T. Kupfer, Angew. Chem., Int. Ed., 2008, 47, 10 (a) T. Heitkemper and C. P. Sindlinger, Chem.–Eur. J., 2019,
1
951–1954; (c) J. H. Barnard, S. Yruegas, K. Huang and
25, 6628–6637; (b) Z. L. Zhang, R. M. Edkins, M. Haehnel,
M. Wehner, A. Eichhorn, L. Mail ¨a nder, M. Meier, J. Brand,
F. Brede, K. M u¨ ller-Buschbaum, H. Braunschweig and
T. B. Marder, Chem. Sci., 2015, 6, 5922–5927.
C. D. Martin, Chem. Commun., 2016, 52, 9985–9991; (d)
A. Steffen, R. M. Ward, W. D. Jones and T. B. Marder,
Coord. Chem. Rev., 2010, 254, 1950–1976.
3
4
P. J. Fagan, E. G. Burns and J. C. Calabrese, J. Am. Chem. Soc., 11 (a) H. Braunschweig, C. W. Chiu, A. Damme, K. Ferkinghoff,
1988, 110, 2979–2981.
K. Kra, K. Radacki and J. Wahler, Organometallics, 2011, 30,
3210–3216; (b) H. Braunschweig, C. W. Chiu, J. Wahler,
K. Radacki and T. Kupfer, Chem.–Eur. J., 2010, 16, 12229–
12233; (c) Z. L. Zhang, Z. Wang, M. Haehnel, A. Eichhorn,
R. M. Edkins, A. Steffen, A. Krueger, Z. Y. Lin and
T. B. Marder, Chem. Commun., 2016, 52, 9707–9710; (d)
Z. Wang, Y. Zhou, K. H. Lee, W. H. Lam, R. D. Dewhurst,
H. Braunschweig, T. B. Marder and Z. Y. Lin, Chem.–Eur. J.,
2017, 23, 11587–11597.
(a) G. E. Herberich, B. Buller, B. Hessner and W. Oschmann,
J. Organomet. Chem., 1980, 195, 253–259; (b) C. W. So,
D. Watanabe, A. Wakamiya and S. Yamaguchi,
Organometallics, 2008, 27, 3496–3501; (c) C. Sindlinger and
P. N. Ruth, Angew. Chem., Int. Ed., 2019, 58, 15051–15056.
(a) C. Baldock, J. B. Rafferty, S. E. Sedelnikova, P. J. Baker,
A. R. Stuitje, A. R. Slabas, T. R. Hawkes and D. W. Rice,
Science, 1996, 274, 2107–2110; (b) L. J. Liu, A. J. V. Marwitz,
5
B. W. Matthews and S. Y. Liu, Angew. Chem., Int. Ed., 2009, 12 (a) P. J. Fagan, W. A. Nugent and J. C. Calabrese, J. Am. Chem.
4
8, 6817–6819; (c) D. H. Knack, J. L. Marshall,
Soc., 1994, 116, 1880–1889; (b) G. E. Herberich and H. Ohst,
Chem. Ber., 1985, 118, 4303–4313.
G. P. Harlow, A. Dudzik, M. Szaleniec, S. Y. Liu and
J. Heider, Angew. Chem., Int. Ed., 2013, 52, 2599–2601; (d) 13 J. J. Baker, K. H. M. Al Furaiji, O. T. Liyanage, D. J. D. Wilson,
S. Jinna and J. Finch, Drug Des. Dev. Ther., 2015, 9, 6185–
190; (e) A. S. Paller, W. L. Tom, M. G. Lebwohl,
J. L. Dutton and C. D. Martin, Chem.–Eur. J., 2019, 25, 1581–
1587.
6
R. L. Blumenthal, M. Boguniewicz, R. S. Call, 14 (a) G. E. Herberich, B. Hessner, H. Ohst and I. A. Raap, J.
L. F. Eicheneld, D. W. Forsha, W. C. Rees, E. L. Simpson,
M. C. Spellman, L. F. S. Gold, A. L. Zaenglein,
Organomet. Chem., 1988, 348, 305–316; (b) G. E. Herberich,
M. Negele and H. Ohst, Chem. Ber., 1991, 124, 25–29.
M. H. Hughes, L. T. Zane and A. A. Hebert, J. Am. Acad. 15 (a) M. J. D. Bosdet and W. E. Piers, Can. J. Chem., 2009, 87, 8–
Dermatol., 2016, 75, 494–503.
29; (b) P. G. Campbell, A. J. V. Marwitz and S. Y. Liu, Angew.
130 | Chem. Sci., 2020, 11, 126–131
This journal is © The Royal Society of Chemistry 2020