Organic Letters
Letter
Xu, H.; Chen, Y.-Q.; Dai, H.-X.; Yu, J.-Q. J. Am. Chem. Soc. 2016, 138,
2146. (f) Jiang, H.; He, J.; Liu, T.; Yu, J.-Q. J. Am. Chem. Soc. 2016,
138, 2055.
(c) Katayev, D.; Larionov, E.; Nakanishi, M.; Besnard, C.; Kundig, E.
P. Chem. - Eur. J. 2014, 20, 15021.
(21) Holstein, P. M.; Vogler, M.; Larini, P.; Pilet, G.; Clot, E.;
Baudoin, O. ACS Catal. 2015, 5, 4300.
̈
(5) Talele, T. T. J. Med. Chem. 2016, 59, 8712.
(22) For recent examples of bisphosphine monoxides in asymmetric
(6) (a) Ladd, C. L.; Sustac Roman, D.; Charette, A. B. Org. Lett.
2013, 15, 1350. (b) Roman, D. S.; Charette, A. B. Org. Lett. 2013, 15,
4394. For other examples of cyclopropane direct arylation, see:
(c) Saget, T.; Cramer, N. Angew. Chem., Int. Ed. 2012, 51, 12842.
(d) Pedroni, J.; Saget, T.; Donets, P. A.; Cramer, N. Chem. Sci. 2015, 6,
5164. (e) Lee, T.; Hartwig, J. F. Angew. Chem. 2016, 128, 8865.
(f) Chan, K. S. L.; Fu, H.-Y.; Yu, J.-Q. J. Am. Chem. Soc. 2015, 137,
2042.
catalysis, see: (a) Woste, T. H.; Oestreich, M. Chem. - Eur. J. 2011, 17,
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11914. (b) Wu, C.; Zhou, J. J. Am. Chem. Soc. 2014, 136, 650.
(c) Borrajo-Calleja, G. M.; Bizet, V.; Mazet, C. J. Am. Chem. Soc. 2016,
138, 4014.
(23) Pedroni, J.; Cramer, N. Angew. Chem., Int. Ed. 2015, 54, 11826.
(24) de Vries, A. H. M.; Meetsma, A.; Feringa, B. L. Angew. Chem.,
Int. Ed. Engl. 1996, 35, 2374.
(25) It is probable that either competing background reactions from
acetate or the activity of the bisphosphine bisoxide is responsible for
diminished enantioselectivities. We will report more details in due
course.
(7) Ladd, C. L.; Belouin, A. V.; Charette, A. B. J. Org. Chem. 2016, 81,
256.
(8) For reports on the role of acetate to mediate concerted-
metalation deprotonation, see: (a) Ackermann, L. Chem. Rev. 2011,
111, 1315. (b) Lapointe, D.; Fagnou, K. Chem. Lett. 2010, 39, 1118.
(9) Previous reports have speculated on the use of bidentate ligands
in Pd-catalyzed intramolecular arylation. See: (a) Pascual, S.; de
Mendoza, P.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M.
Tetrahedron 2008, 64, 6021. (b) García-Cuadrado, D.; Braga, A. A. C.;
Maseras, F.; Echavarren, A. M. J. Am. Chem. Soc. 2006, 128, 1066.
(10) Only starting material was observed. 88% starting material was
recovered for 1h. An intermolecular competition/doping experiment
between 1a and 1h suggests catalyst sequestration is not occurring (see
(11) Starting material was recovered. Poor reactivity may be
attributed to catalyst poisoning. For other reports on α-substitution
on direct functionalization, see: Gutekunst, W. R.; Baran, P. S. J. Org.
Chem. 2014, 79, 2430.
(12) (a) Ladd, C. L.; Roman, D. S.; Charette, A. B. Tetrahedron 2013,
69, 4479. (b) Rousseaux, S.; Lieg
3, 244.
́
ault, B.; Fagnou, K. Chem. Sci. 2012,
(13) The ring-opened product was formed exclusively; no signs of
the cyclopropyl-fused product were observed. We are currently
exploring this transformation.
(14) (a) Li, H.; Belyk, K. M.; Yin, J.; Chen, Q.; Hyde, A.; Ji, Y.;
Oliver, S.; Tudge, M. T.; Campeau, L.-C.; Campos, K. R. J. Am. Chem.
Soc. 2015, 137, 13728. (b) Ji, Y.; Plata, R. E.; Regens, C. S.; Hay, M.;
Schmidt, M.; Razler, T.; Qiu, Y.; Geng, P.; Hsiao, Y.; Rosner, T.;
Eastgate, M. D.; Blackmond, D. G. J. Am. Chem. Soc. 2015, 137, 13272.
(15) Co
2004, 43, 6525. Boezio, A. A.; Pytkowicz, J.; Co
Am. Chem. Soc. 2003, 125, 14260.
̂
te,
́
A.; Boezio, A. A.; Charette, A. B. Angew. Chem., Int. Ed.
̂
te, A.; Charette, A. B. J.
́
(16) It has been well-established that BINAP can be oxidized to
BINAP(O) using Pd(II) and base. See: (a) Grushin, V. V.
Organometallics 2001, 20, 3950. (b) Marshall, W. J.; Grushin, V. V.
Organometallics 2003, 22, 555. (c) Shimizu, I.; Matsumoto, Y.; Shoji,
K.; Ono, T.; Satake, A.; Yamamoto, A. Tetrahedron Lett. 1996, 37,
7115. For a review on bisphosphine monoxides, see: Grushin, V. V.
Chem. Rev. 2004, 104, 1629.
(17) Pivalate is known to promote reactivity when acetate is
ineffective. See: (a) Lafrance, M.; Gorelsky, S. I.; Fagnou, K. J. Am.
Chem. Soc. 2007, 129, 14570. (b) Lafrance, M.; Lapointe, D.; Fagnou,
K. Tetrahedron 2008, 64, 6015. Dba has been known to impede
reactivity. See: (c) Amatore, C.; Broeker, G.; Jutand, A.; Khalil, F. J.
Am. Chem. Soc. 1997, 119, 5176. (d) Amatore, C.; Jutand, A. Coord.
Chem. Rev. 1998, 178−180, 511.
(18) (a) Wasa, M.; Chan, K. S. L.; Zhang, X.-G.; He, J.; Miura, M.;
Yu, J.-Q. J. Am. Chem. Soc. 2012, 134, 18570. (b) For a review, see:
Engle, K. M.; Yu, J.-Q. J. Org. Chem. 2013, 78, 8927.
(19) (a) Albicker, M. R.; Cramer, N. Angew. Chem., Int. Ed. 2009, 48,
9139. For reviews, see: (c) Teichert, J. F.; Feringa, B. L. Angew. Chem.,
Int. Ed. 2010, 49, 2486. (d) Pedroni, J.; Cramer, N. Chem. Commun.
2015, 51, 17647.
(20) (a) Nakanishi, M.; Katayev, D.; Besnard, C.; Kundig, E. P.
̈
Angew. Chem., Int. Ed. 2011, 50, 7438. (b) Larionov, E.; Nakanishi, M.;
Katayev, D.; Besnard, C.; Kundig, E. P. Chem. Sci. 2013, 4, 1995.
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