Journal of the American Chemical Society
Communication
(11) (a) Midland, M. M.; Preston, S. B. J. Am. Chem. Soc. 1982, 104,
2330. (b) Brown, H. C.; Jayaraman, S. J. Org. Chem. 1993, 58, 6791
Generality and scope of these methods either is limited by borinic acid
method of generation (ref 10a) or is nonselective (ref 10b).
(12) Denmark, S. E.; Beutner, G. L. Angew. Chem., Int. Ed. 2008, 47,
1560.
(13) (a) Stymiest, J. L.; Dutheuil, G.; Mahmood, A.; Aggarwal, V. K.
Angew. Chem., Int. Ed. 2007, 46, 7491. (b) Webster, M. P.; Partridge, B.
M.; Aggarwal, V. K. Org. Synth. 2011, 88, 247. (c) Larouche-Gauthier,
R.; Fletcher, C. J.; Couto, I.; Aggarwal, V. K. Chem. Commun. 2011, 47,
12592. (d) Zschage, O.; Hoppe, D. Angew. Chem., Int. Ed. 1989, 28, 69.
(14) The α-products (1:1 mixture of diastereomers) originate from
1,3-borotropic shift followed by allylation:
Doctoral Training Centre and GSK for support. We thank Dr.
David Hirst (GSK) for support of the DTC project.
REFERENCES
(1) First published: (a) Blais, J.; L’Honore,
■
́
A.; Soulie,
́
J.; Cadiot, P. J.
Organomet. Chem. 1974, 78, 323. (b) Chemler, S. R.; Roush, W. R.
Recent applications of the allylation reaction to the synthesis of natural
products. Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH:
Weinheim, 2000, pp 403−490. (c) Yamamoto, Y.; Asao, N. Chem. Rev.
1993, 93, 2207. (d) Hoffmann, R. W. Pure Appl. Chem. 1988, 60, 123.
(e) Lachance, H.; Hall, D. G. Allylboration of Carbonyl Compounds.
Organic Reactions; Denmark, S. E., Ed.; John Wiley & Sons: New York,
2008, pp 1−573; (f) Kennedy, J. W. J.; Hall, D. G. Recent advances in
the preparation of allylboronates and their use in tandem reactions
with carbonyl compounds. Boronic Acids; Hall, D. G., Ed.; Wiley-VCH:
Weinheim, 2005, pp 241−274.
(2) (a) Hoffmann, R. W.; Zeiβ, H.-J. Angew. Chem., Int. Ed. Engl.
1979, 18, 306. (b) Hoffmann, R. W.; Zeiβ, H.-J. J. Org. Chem. 1981,
46, 1309. (c) Hoffmann, R. W. Pure Appl. Chem. 1988, 60, 123.
(d) Hoffmann, R. W.; Niel, G.; Schlapbach, A. Pure Appl. Chem. 1990,
62, 1993.
(3) (a) Brown, H. C.; Jadhav, P. K. J. Am. Chem. Soc. 1983, 105,
2092. (b) Brown, H. C.; Bhat, K. S. J. Am. Chem. Soc. 1986, 108, 293.
(c) Ramachandran, P. V. Aldrichimica Acta 2002, 35, 23.
(4) The 2008 comprehensive review of allylation reaction using
allylboron reagents by D. G. Hall (ref 1e) cites 49 pages of tabulated
individual reactions using α-substituted allylboron reagents compared
to 419 pages of reactions using allylboron reagents without α-
substitution.
(5) (a) Kramer, G. W.; Brown, H. C. J. Organomet. Chem. 1977, 132,
9. (b) Bubnov, Y. N.; Gurskii, M. E.; Gridnev, I. D.; Ignatenko, A. V.;
Ustynyuk, Y. A.; Mstislavsky, V. I. J. Organomet. Chem. 1992, 424, 127.
(6) In certain cases this can be controlled: (a) Hancock, K. G.;
Kramer, J. D. J. Am. Chem. Soc. 1973, 6463. (b) Chen, M.; Handa, M.;
Roush, W. R. J. Am. Chem. Soc. 2009, 131, 14602. (c) Kister, J.;
DeBaillie, A. C.; Lira, R.; Roush, W. R. J. Am. Chem. Soc. 2009, 131,
14174. (d) Gonzalez, A. Z.; Roman, J. G.; Alicea, E.; Canales, E.;
Soderquist, J. A. J. Am. Chem. Soc. 2009, 131, 1269. (e) Fang, G. Y.;
Aggarwal, V. K. Angew. Chem., Int. Ed. 2007, 46, 359. (f) Brown, H. C.;
Jadhav, P. K.; Bhat, K. S. J. Am. Chem. Soc. 1985, 107, 2564.
(7) Althaus, M.; Mahmood, A.; Suarez, J. R.; Thomas, S. P.;
Aggarwal, V. K. J. Am. Chem. Soc. 2010, 132, 4025.
(15) (a) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett.
1990, 40, 4289. (b) Batey, R. A.; Thadani, A. N.; Smil, D. V. Synthesis
2000, 990.
(16) A single report by Morken describing allylboration of related β-
boryl α-substituted pinacol boronic esters where high Z selectivity was
also observed: Woodward, A. R.; Burks, H. E.; Chan, L. M.; Morken, J.
P. Org. Lett. 2005, 7, 5505.
(17) Protodeboronation of these substrates also led to high Z
selectivity (>95:5). Both allylboration and protodeboronation are
believed to occur through similar transition states. For a discussion
see: Hesse, M. J.; Butts, C. P.; Willis, C. L.; Aggarwal, V. K. Angew.
Chem., Int. Ed. 2012, 51, 12444 . High Z-selectivity observed is due to
(dominant) gauche interactions of the α-substituent with the pinacol
ester together with enhanced A1,2-strain associated with methallyl
boronic esters: .
(18) Chemical shift in accordance with borinic esters found in
literature: Cole, T. E.; Haly, B. D. Organometallics 1992, 11, 652.
(19) 11B NMR has also been used to analyse the intermediates
formed when AcCl or CCl3COCl is used as the additive (in place of
TFAA) in the allylation. In both cases, 11B NMR analysis of the
intermediate formed showed a signal at ∼51 ppm. The fact that the
use of all three additives result in the formation of intermediates with
similar signals in the 11B NMR indicates that the intermediate is a
pinacolate-derived borinic ester (partially ring-opened) and not an
intermediate with complete displacement of the pinacolate by the acid
derivative (TFA−/Cl−). We thank one of the reviewers for providing
this suggestion.
(20) Chemical shifts in accordance with those found in the literature:
2012).
(21) See SI for details.
(22) Shiner, C. S.; Garner, C. M.; Haltiwanger, R. C. J. Am. Chem.
Soc. 1985, 107, 7167.
(8) (a) Flamme, E. M.; Roush, W. R. J. Am. Chem. Soc. 2002, 124,
13644. (b) Pietruszka, J.; Schone, N. Eur. J. Org. Chem. 2004, 5011.
̈
(c) Pietruszka, J.; Schone, N. Synthesis 2006, 24. (d) Cmrecki, V.;
̈
Eichenauer, N. C.; Frey, W.; Pietruszka, J. Tetrahedron 2010, 66, 6550.
(9) (a) Hoffmann, R. W.; Weidmann, U. J. Organomet. Chem. 1980,
195, 137. (b) Andersen, M. W.; Hildebrandt, B.; Kosher, G.;
Hoffmann, R. W. Chem. Ber 1989, 122, 1777. (c) Carosi, L.;
Lachance, H.; Hall, D. G. Tetrahedron Lett. 2005, 46, 8981. Use of
Lewis acids has provided high E selectivity for α-alkyl substituted
pinacol boronic esters: (d) Peng, F.; Hall, D. G. Tetrahedron Lett.
2007, 48, 3305. (e) Peng, F.; Hall, D. G. J. Am. Chem. Soc. 2007, 129,
3070. (f) Ito, H.; Ito, S.; Sasaki, Y.; Matsuura, K.; Sawamura, M. J. Am.
Chem. Soc. 2007, 129, 14856. (g) Chen, M.; Roush, W. R. Org. Lett.
2010, 12, 2706.
(10) (a) Matteson, D. S.; Ray, R. J. Am. Chem. Soc. 1980, 102, 7590.
(b) Pelz, N. F.; Woodward, A. R.; Burks, H. E.; Sieber, J. D.; Morken,
J. P. J. Am. Chem. Soc. 2004, 126, 16328. (c) Beckmann, E.; Desai, V.;
Hoppe, D. Synlett 2004, 2275. (d) Carosi, L.; Hall, D. G. Angew.
Chem., Int. Ed. 2007, 46, 5913. (e) Guzman-Martinez, A.; Hoveyda, A.
H. J. Am. Chem. Soc. 2010, 132, 10634. (f) Park, J. K.; Lackey, H. H.;
Ondrusek, B. A.; McQuade, D. T. J. Am. Chem. Soc. 2011, 133, 2410.
(g) Pulis, A.; Aggarwal, V. K. J. Am. Chem. Soc. 2012, 135, 7570.
(h) Sonawane, R. P.; Jheengut, V.; Larouche-Gauthier, R.;
Rampalakos, K.; Scott, H. K.; Aggarwal, V. K. Angew. Chem., Int. Ed.
2011, 50, 3760. (i) Posseme, F.; Deligny, M.; Carreaux, F.; Carboni, B.
J. Org. Chem. 2007, 72, 984. (j) Kliman, L. T.; Mlynarski, S. N.; Ferris,
G. E.; Morken, J. P. Angew. Chem., Int. Ed. 2012, 51, 521.
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