Please do not adjust margins
ChemComm
Page 4 of 5
DOI: 10.1039/C8CC00754C
COMMUNICATION
Journal Name
Ed. 2008, 47, 258; (c) I. G. Rios, A. Rosas‐Hernandez and E.
Martin, Molecules 2011, 16, 970.
lithium phenoxide acted as a bifunctional chiral catalyst (i.e., the
Pd center activated the electrophilic allyl acetate
phenoxide activated the silyl enolate of ). Control experiments
supported this unique synergistic reaction mechanism.18 The
present work provides an entirely different application of (S)‐
2 and lithium
9
(a) M. Sjöegren, S. Hansson, P.‐O. Norrby, B. Åkermark, M. E.
Cucciolito and A. Vitagliano, Organometallics 1992, 11, 3954;
(b) S. Hansson, P.‐O. Norrby, M. P. T. Sjöegren and B.
Åkermark Organometallics 1993, 12, 4940; (c) M. P. T.
Sjöegren, S. Hansson, B. Åkermark and A. Vitagliano,
Organometallics 1994, 13, 1963; (d) B. Åkermark and S.
Hansson, J. Am. Chem. Soc. 1990, 112, 4587; (e) M. Bosch and
M. Schlaf, J. Org. Chem. 2003, 68, 5225.
3
1
,
which has been investigated as an N,N,O‐tridentate ligand,6,7
and can provide an addition to the set of bifunctional chiral
ligands.
This research was supported by Grants‐in‐Aid for Scientific
Research from the Japan Society for the Promotion of Science
(Nos. 15H03808, 15K21063).
10 (a) E. Peña‐Cabrera, P.‐O. Norrby, M. Sjögren, A. Vitagliano, V.
De Felice, J. Oslob, S. Ishii, D. O'Neill, B. Åkermark and P.
Helquist, J. Am. Chem. Soc. 1996, 118, 4299; (b) G. Chelucci,
V. Caria and A. Saba, J. Mol. Catal. A: Chem. 1998, 130, 51; (c)
G. Chelucci and A. Saba, Tetrahedron: Asymmetry 1998, 9,
2575; (d) G. Chelucci, G. A. Pinna, A. Saba and G. Sanna, J. Mol.
Catal. A: Chem. 2000, 159, 423.
Conflicts of interest
11 Reviews, see: (a) Lewis Base Catalysis in Organic Synthesis
(Eds.: E. Vedejs and S. E. Denmark), Wiley‐VCH, Weinheim,
2016; (b) S. E. Denmark and G. L. Beutner, Angew. Chem. Int.
Ed. 2008, 47, 1560; (c) J. Gawronski, N. Wascinska and J.
Gajewy, Chem. Rev. 2008, 108, 5227‐5252; (d) R. L. Sutar and
N. N. Joshi, Tetrahedron: Asymmetry 2013, 24, 1345.
There are no conflicts to declare.
Notes and references
1
2
3
(a) N. Kumagai, M. Kanai and H. Sasai, ACS Catal. 2016, 6, 4699
12 D. Bourgeois, D. Craig, N. P. King and D. M. Mountford,
Angew. Chem. Int. Ed. 2005, 44, 618.
and references therein; (b) Cooperative Catalysis: Designing
Efficient Catalysts for Synthesis (Ed.: R. Peters) Wiley‐VCH,
Weinheim, 2015; (c) Topics in Organometallics Chemistry ‐
Bifunctional Molecular Catalysis (Eds. T. Ikariya and M.
Shibasaki) Springer, Berlin, 2011.
13 Examples of the activation of silyl enolate by alkali metal
phenoxide as Lewis base catalyst, see: (a) Y. Orito, S.
Hashimoto, T. Ishizuka and M. Nakajima, Tetrahedron 2006,
62, 390; (b) M. Hatano, E. Takagi and K. Ishihara, Org. Lett.
Recent reviews, see: (a) N. Kurono and T. Ohkuma, ACS Catal.
2016, 6, 989; (b) H. Pellissier, Adv. Synth. Catal. 2015, 357,
857; (c) R. M. Haak, S. J. Wezenberg and A. W. Kleij, Chem.
Commun. 2010, 46, 2713; (d) C. Nájera, J. M. Sansano and J.
M. Saá, Eur. J. Org. Chem. 2009, 2385; (e) L. M. Geary and P.
G. Hultin, Tetrahedron: Asymmetry 2009, 20, 131.
2007, 9, 4527.
14 Examples of the activation of silyl enolate by LiOAc as Lewis
base catalyst, see: (a) T. Nakagawa, H. Fujisara and T.
Mukaiyama, Chem. Lett. 2003, 32, 462; (b) T. Nakagawa, H.
Fujisara and T. Mukaiyama, Chem. Lett. 2003, 32, 696; (c) T.
Nakagawa, H. Fujisara, Y. Nagata and T. Mukaiyama, Bull.
Chem. Soc. Jpn. 2004, 77, 1555; (d) H. Fujisawa, E. Takahashi
and T. Mukaiyama, Chem. Eur. J. 2006, 12, 5082.
Recent examples, see: (a) K. Latendorf, M. Mechler, I.
Schamne, D. Mack, W. Frey and R. Peters, Eur. J. Org. Chem.
2017, 28, 4140; (b) D. Brodbeck, F. Broghammer, J. Meisner,
J. Klepp, D. Garnier, W. Frey, J.Kästner and R. Peters, Angew.
Chem. Int. Ed. 2017, 56, 4056; (c) M. Weiss, J. Holz and R.
Peters, Eur. J. Org. Chem. 2016, 210; (d) M. Mechler and R.
Peters, Angew. Chem. Int. Ed. 2015, 54, 10303; (e) M. Katari,
G. Rajaraman and P. Ghosh, Adv. J. Organomet. Chem. 2015,
775, 109; (f) S. E. Song, Q. T. Nguyen, J. J. Yu, H.‐I. Lee and J.
H. Jeong, Polyhedron 2014, 67, 264; (g) P. Meier, F.
Broghammer, K. Latendorf, G. Rauhut and R. Peters,
Molecules 2012, 17, 7121; (h) Y.‐Q. Wen, W.‐M. Ren and X.‐B.
15 TMS‐protected (S)‐1a was prepared by the reaction of (S)‐1a
and BSA in MeCN according to the literature (H. Noda and J.
W. Bode J. Am. Chem. Soc. 2015, 137, 3958.). After the
removal of MeCN, TMS‐protected (S)‐1a was used in
asymmetric allylic substitution without further purifications
due to the poor stability in silica gel column chromatography.
16 Silylation of hydroxyl or amino group in chiral ligand was
observed in Pd‐catalyzed allylic substitution with BSA. (a) Y.
Tanaka, T. Mino, K. Akita, M. Sakamoto and T. Fujita, J. Org.
Chem. 2004, 69, 6679; (b) T. Nemoto, T. Matsumoto, T.
Masuda, T. Hitomi, K. Hatano and Y. Hamada, J. Am. Chem.
Soc. 2004, 126, 3690.
Lu, Org. Biomol. Chem. 2011, 9, 6323; (i) I. D. Gridnev, M.
Watanabe, H. Wang and T. Ikariya, J. Am. Chem. Soc. 2010,
132, 1663.
(a) A. Bencini and V. Lippolis, Coord. Chem. Rev. 2010, 254
2096; (b) P. G. Sammes and G. Yahioglu, Chem. Soc. Rev. 1994,
23, 327; (c) L. A. Summers, Adv. Heterocycl. Chem. 1978, 22
17 LiOAc‐catalyzed desilylation of siloxy phenol was reported. B.
Wang, H.‐X. Sun and Z.‐H. Sun, J. Org. Chem. 2009, 74, 1781.
18 For further details on the mechanistic studies in revision of
this manuscript, see ESI.
4
,
,
1; (d) C. R. Luman and F. N. Castellano, Comprehensive
Coordination Chemistry II, Vol. 1 (Eds.: J. A. McCleverty and T.
J. Meyer), Elsevier, Oxford, UK, 2004, pp. 25‐39.
5
6
7
E. Schoffers, Eur. J. Org. Chem. 2003, 1145.
Y. Naganawa and H. Nishiyama Chem. Rec. 2016, 16, 2573.
(a) Y. Naganawa, T. Namba, T. Aoyama, K. Shoji and H.
Nishiyama, Chem. Commun. 2014, 50
, 13224; (b) Y.
Naganawa, H. Komatsu and H. Nishiyama, Chem. Lett. 2015,
44, 1652; (c) Y. Naganawa, T. Aoyama and H. Nishiyama, Org.
Biomol. Chem. 2015, 13, 11499; (d) Y. Naganawa, T. Aoyama,
K. Kato and H. Nishiyama, ChemitrySelect 2016, 1, 1938; (e) Y.
Naganawa, T. Namba, M. Kawagishi and H. Nishiyama, Chem.
Eur. J. 2015, 21, 9319; (f) Y. Naganawa, H. Abe and H.
Nishiyama, Synlett 2016, 27, 1973.
Reviews, see: (a) B. M. Trost and D. L. Van Vranken, Chem.
Rev. 1996, 96, 395; (b) Z. Lu and S. M. Ma, Angew. Chem. Int.
8
4 | J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins