Journal of the American Chemical Society
Communication
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without catalyst. Future studies will be aimed at elucidating the
kinetic product.
Organometallics 1993, 12, 975. (c) Coapes, R. B.; Souza, F. E. S.;
Thomas, R. L.; Hall, J. J.; Marder, T. B. Chem. Commun. 2003, 614.
(d) Mkhalid, I. A. I.; Coapes, R. B.; Edes, S. N.; Coventry, D. N.; Souza,
In conclusion, we have demonstrated the first example of a
boryl-Heck reaction using an electrophilic boron reagent. This
transformation converts terminal alkenes to alkenyl boronic
esters and their derivatives in high yield and with good
functional group tolerance. The reaction is compatible with both
linear α-olefin and styrenyl substrates and provides products
with excellent E/Z ratios. This work demonstrates that
identification of a bulky amine base, in combination with
appropriate catalyst and additives, overcomes the previously
observed incompatibility of chloroboranes with conditions that
enable β-hydride elimination. By harnessing a Heck mechanism,
this method enables use of an inexpensive, readily available
borylating reagent and avoids formation of byproducts, two
significant advantages over existing methods to deliver these
valuable versatile synthetic intermediates.
F. E. S.; Thomas, R. L.; Hall, J. J.; Bi, S.-W.; Lin, Z.; Marder, T. B.
Dalton Trans. 2008, 1055. (e) Takaya, J.; Kirai, N.; Iwasawa, N. J. Am.
Chem. Soc. 2011, 133, 12980. (f) Kirai, N.; Iguchi, S.; Ito, T.; Takaya, J.;
Iwasawa, N. Bull. Chem. Soc. Jpn. 2013, 86, 784. (g) Brown, J. M.;
Lloyd-Jones, G. C. J. Chem. Soc., Chem. Commun. 1992, 710. (h) Brown,
J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (i) Murata,
M.; Watanabe, S.; Masuda, Y. Tetrahedron Lett. 1999, 40, 2585.
(j) Murata, M.; Kawakita, K.; Asana, T.; Watanabe, S.; Masuda, Y. Bull.
Chem. Soc. Jpn. 2002, 75, 825. (k) Iwadate, N.; Suginome, M. Chem.
Lett. 2010, 39, 558. (l) Morimoto, M.; Miura, T.; Murakami, M. Angew.
Chem., Int. Ed. 2015, 54, 12659. (m) Mkhalid, I. A. I.; Barnard, J. H.;
Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890.
(
9) Anastasi, N. R.; Waltz, K. M.; Weerakoon, W. L.; Hartwig, J. F.
Organometallics 2003, 22, 365.
10) (a) Onozawa, S.-y.; Tanaka, M. Organometallics 2001, 20, 2956.
(
Also see: (b) Braunschweig, H.; Gruss, K.; Radacki, K.; Uttinger, K. Eur.
J. Inorg. Chem. 2008, 2008, 1462.
(11) (a) Daini, M.; Suginome, M. J. Am. Chem. Soc. 2011, 133, 4758.
ASSOCIATED CONTENT
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b) Daini, M.; Yamamoto, A.; Suginome, M. J. Am. Chem. Soc. 2008,
30, 2918. (c) Yamamoto, A.; Suginome, M. J. Am. Chem. Soc. 2005,
27, 15706.
*
S
Supporting Information
(12) Daini, M.; Suginome, M. Chem. Commun. 2008, 5224.
Crystallographic and data (CIF)
(13) In one case, a cascade cyclization has been reported that is
terminated in a Heck-like process after capture of the organometallic
intermediate with styrene; see: Nakada, K.; Daini, M.; Suginome, M.
Chem. Lett. 2013, 42, 538.
(14) Coapes, R. B.; Souza, F. E. S.; Fox, M. A.; Batsanov, A. S.; Goeta,
A. E.; Yufit, D. S.; Leech, M. A.; Howard, J. A. K.; Scott, A. J.; Clegg, W.;
Marder, T. B. J. Chem. Soc., Dalton Trans. 2001, 1201.
AUTHOR INFORMATION
(15) (a) McAtee, J. R.; Martin, S. E. S.; Ahneman, D. T.; Johnson, K.
Notes
A.; Watson, D. A. Angew. Chem., Int. Ed. 2012, 51, 3663. (b) Martin, S.
E. S.; Watson, D. A. J. Am. Chem. Soc. 2013, 135, 13330. (c) Martin, S.
E. S.; Watson, D. A. Synlett 2013, 24, 2177. (d) McAtee, J. R.; Martin, S.
E. S.; Cinderella, A. P.; Reid, W. B.; Johnson, K. A.; Watson, D. A.
Tetrahedron 2014, 70, 4250. (e) McAtee, J. R.; Yap, G. P. A.; Watson,
D. A. J. Am. Chem. Soc. 2014, 136, 10166. (f) McAtee, J. R.; Krause, S.
B.; Watson, D. A. Adv. Synth. Catal. 2015, 357, 2317.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The University of Delaware (UD), the Research Corporation
Cottrell Scholars Program), and the NSF (CAREER
CHE1254360) are gratefully acknowledged for support. J.J.S.
acknowledges UD for Summer Scholars Fellowships. Dr. Glenn
Yap is thanked for crystallography and Dr. Olga Dmytrenko for
help with calculations. NMR and other data were acquired at
UD on instruments obtained with the assistance of NSF and
NIH funding (NSF CHE0421224, CHE1229234,
CHE0840401, and CHE1048367; NIH P20GM104316,
P30GM110758, S10RR02692 and S10OD016267).
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16) Gerrard, W.; Lappert, M. F.; Mountfield, B. A. J. Chem. Soc. 1959,
529.
17) For recent uses of catBCl see: (a) Hirner, J. J.; Faizi, D. J.; Blum,
1
(
S. A. J. Am. Chem. Soc. 2014, 136, 4740. (b) Faizi, D. J.; Issaian, A.;
(19) L1 is commerically avaliable from Aspira Scientific, Milpitas, CA.
(20) The reason for the superiority of L1 is not immediately obvious.
However, Marder has shown that highly nucleophilic phosphines
complex catBCl, and less basic phosphines can decompose it; see ref 14.
We suspect that L1 has the correct balance of electron-donor ability to
support a highly active palladium catalyst, but is sterically hindered
enough to prevent decomposition or deactivation of the boron reagent
in situ.
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(21) At present we do not understand the role of LiOTf in
(
suppressing alkene isomerization, but suspect that the limited solubilty
of LiCl in PhCF3 might be important in controlling unfavorable
palladium hydride equilibria in the reaction.
(
(
(
22) Added LiI increases isomerization with nonstyrenyl substrates.
23) To date, other disubstituted alkenes have provided much lower
(
yield in this reaction. These substrates are the subject of current
investigations.
(
(
4
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J. Am. Chem. Soc. XXXX, XXX, XXX−XXX