Organic Letters
Letter
36, 1082. (e) Takai, K. In Comprehensive Organic Synthesis, 2nd ed.;
Molander, G. A.; Knochel, P., Eds.; Elsevier: Oxford, 2014; Vol. 1, p 159.
(6) Murai, M.; Taniguchi, R.; Hosokawa, N.; Nishida, Y.; Mimachi, H.;
Oshiki, T.; Takai, K. J. Am. Chem. Soc. 2017, 139, 13184.
(7) For representative reviews on gem-dimetallomethanes, see:
(a) Marek, I.; Normant, J.-F. Chem. Rev. 1996, 96, 3241. (b) Marek, I.
Chem. Rev. 2000, 100, 2887. (c) Matsubara, S.; Oshima, K.; Utimoto, K.
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Organozinc ReagentsA Practical Approach; Knochel, P., Jones, P., Eds.;
Oxford University Press: Oxford, 1999; pp 119−137. (e) Normant, J. F.
Acc. Chem. Res. 2001, 34, 640.
electron-rich olefins, which were not applicable to iodo- and
silylcyclopropanation in our previous work, reacted smoothly to
provide the corresponding borylcyclopropanes in good yield.
The compactness and electron-deficient nature of the
pinacolylboryl group attached to the chromocarbene intermedi-
ate was key for clarifying the novel reactivity of the gem-
dimetallomethanes. The current reaction proceeds under mild
conditions with good stereoselectivity and functional group
tolerance, and therefore will be useful in the total synthesis of
natural products.
(8) (a) Zhou, S.-M.; Deng, M.-Z.; Xia, L.-J.; Tang, M.-H. Angew. Chem.,
Int. Ed. 1998, 37, 2845. (b) Wallace, D. J.; Chen, C. Tetrahedron Lett.
2002, 43, 6987. (c) Pietruszka, J.; Witt, A.; Frey, W. Eur. J. Org. Chem.
2003, 2003, 3219.
(9) For representative examples, see: (a) Rubina, M.; Rubin, M.;
Gevorgyan, V. J. Am. Chem. Soc. 2003, 125, 7198. (b) Charette, A. B.;
Mathieu, S.; Fournier, J.-F. Synlett 2005, 1779 and references therein.
(c) Shimizu, M.; Schelper, M.; Nagao, I.; Shimono, K.; Kurahashi, T.;
Hiyama, T. Chem. Lett. 2006, 35, 1222. (d) Kurahashi, T.; Kozhushkov,
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
X-ray crystallographic data of complex 1j (CIF)
Experimental procedures, spectroscopic data for all new
compounds, copies of 1H and 13C NMR spectra (PDF)
S. I.; Schill, H.; Meindl, K.; Ruhl, S.; de Meijere, A. Angew. Chem., Int. Ed.
̈
2007, 46, 6545. (e) Fujioka, Y.; Amii, H. Org. Lett. 2008, 10, 769. (f) Ito,
H.; Kosaka, Y.; Nonoyama, K.; Sasaki, Y.; Sawamura, M. Angew. Chem.,
AUTHOR INFORMATION
Corresponding Authors
■
Int. Ed. 2008, 47, 7424. (g) Hussain, M. M.; Li, H.; Hussain, N.; Urena,
̃
M.; Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2009, 131, 6516.
(h) Yang, C.-T.; Zhang, Z.-Q.; Tajuddin, H.; Wu, C.-C.; Liang, J.; Liu, J.-
H.; Fu, Y.; Czyzewska, M.; Steel, P. G.; Marder, T. B.; Liu, L. Angew.
Chem., Int. Ed. 2012, 51, 528. (i) Liskey, C. W.; Hartwig, J. F. J. Am.
Chem. Soc. 2013, 135, 3375. (j) Bose, S. K.; Fucke, K.; Liu, L.; Steel, P.
G.; Marder, T. B. Angew. Chem., Int. Ed. 2014, 53, 1799. (k) Murakami,
R.; Tsunoda, K.; Iwai, T.; Sawamura, M. Chem. - Eur. J. 2014, 20, 13127.
ORCID
Notes
́ ́ ́
(l) Parra, A.; Amenos, L.; Guisan-Ceinos, M.; Lopez, A.; Ruano, J. L. G.;
The authors declare no competing financial interest.
Tortosa, M. J. Am. Chem. Soc. 2014, 136, 15833. (m) Miyamura, S.;
Araki, M.; Suzuki, T.; Yamaguchi, J.; Itami, K. Angew. Chem., Int. Ed.
2015, 54, 846. (n) Spencer, J. A.; Jamieson, C.; Talbot, E. P. A. Org. Lett.
2017, 19, 3891.
ACKNOWLEDGMENTS
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This work is financially supported by a Grant-in-Aid (No.
26248030) from MEXT, Japan, and MEXT program for
promoting the enhancement of research universities. The
authors gratefully thank Mr. Masato Kodera and Ms. Seina
Ishihara (Okayama University) for HRMS measurements.
(10) Benoit, G.; Charette, A. B. J. Am. Chem. Soc. 2017, 139, 1364. Our
work was reported in March 2017 (97th CSJ Annual Meeting 2017,
Yokohama, 1E2−18).
(11) Wuts, P. G. M.; Thompson, P. A. J. Organomet. Chem. 1982, 234,
137.
(12) Effect of ligands (monodentate 12 equiv, and bidentate 6 equiv)
with 6 equiv of CrCl2 in THF at 50 °C for 20 h: 1a was not obtained with
Et3N, 2,2′-bipyridyl, 1,2-bis(diphenylphosphino)ethane, or without
ligands. Yield of 1a was 39% with N,N,N′,N′-tetramethyl-1,3-
diaminobutane.
(13) Due to electronic and steric effects, reactivity of alkenes in the
Simmons−Smith reaction is known to diminish in the order of gem-
disubstituted > trisubstituted > tetrasubstituted > cis-disubstituted >
trans-disubstituted > monosubstituted alkenes.
(14) Although yield decreased, a preliminary result for the
borylcyclopropanation of styrene indicated that the amount of CrCl2
could be reduced to 20 mol% using 6 equiv of manganese powder as a
reductant for the (tmeda)CrCl2I B back to (tmeda)CrCl2 A (unreacted
styrene was recovered). A control experiment revealed cyclopropana-
tion did not occur with only manganese in the absence of CrCl2.
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