RSC Advances
Paper
racemization. While TS-2 suffers a severely steric repulsion
K. L. White and K. A. Scheidt, Chem. Sci., 2012, 3, 1205; (l)
Y. P. He, H. T. Hu, X. G. Xie and X. G. She, Tetrahedron,
2013, 69, 559; (m) Y. P. He, B. Ma, J. Yang, X. G. Xie and
X. G. She, Tetrahedron, 2013, 69, 5545; (n) V. Bariak,
A. Malastov ´a , A. Alm ´a ssy and R. Sebesta, Chem.–Eur. J.,
2015, 21, 13445; (o) Y. J. Kwon, Y. K. Jeon, H. B. Sim,
I. Y. Oh, I. Shin and W. S. Kim, Org. Lett., 2017, 19, 6224;
(p) L. Biancalana, S. Zacchini, N. Ferri, M. G. Lupo,
G. Pampaloni and F. Marchetti, Dalton Trans., 2017, 46,
16589.
3 For reviews, see: (a) A. G. Brook, Acc. Chem. Res., 1974, 7, 77;
(b) P. C. Bulman-Page, S. S. Klair and S. Rosenthal, Chem. Soc.
Rev., 1990, 19, 147; (c) P. Jankowski, P. Raubo and J. Wicha,
Synlett, 1994, 985; (d) M. A. Brook, Silicon in Organic,
Organometallic, and Polymer Chemistry, John Wiley and
Sons, New York, 2000; (e) W. H. Moser, Tetrahedron, 2001,
57, 2065; (f) M. Kira and T. Iwamoto, The Chemistry of
Organic Silicon Compounds, Z. Rappoport and Y. Apeloig,
ed. John Wiley and Sons, New York, 2001, pp. 853–948; (g)
E. Schaumann and A. Kirschning, Synlett, 2007, 177; (h)
A. B. Smith and C. M. Adams, Acc. Chem. Res., 2004, 37,
365; (i) H. J. Zhang, D. L. Priebbenow and C. Bolm, Chem.
Soc. Rev., 2013, 42, 8540; (j) M. Sasaki and K. Takeda,
Molecular Rearrangements in Organic Synthesis, ed. C. M.
Rojas, John Wiley and Sons: New York, 2015, pp. 151–183;
(k) G. Eppe, D. Didier and I. Marek, Chem. Rev., 2015, 115,
9175.
1
2
between the Ph group on Si and one of the Ph groups on Si ,
1
the interaction between the Me group on Si and the Ph group
2
on Si appears being tolerable in the case of TS-1. These
ˇ
considerations are supported by the preliminary results from
density functional theory calculations, which showed TS-1 to be
ꢀ
1
more stable than TS-2 by 6.2 kJ mol . Our model also explains
1
the observed steric bias for substituents on Si . Substituents
smaller than the Ph group might not be large enough to create
an appreciable difference between the non-bonded interaction
with the Me group in TS-1 and with the Ph group in TS-2. As
a result, 3 forms with poor diastereoselectivity (Table 1, entries
1–4).
Conclusions
In summary, Si-to-C chirality transfer has been used as an effi-
cient strategy to achieve asymmetric retro-[1,4]-Brook rear-
rangement of 3-silyl allyloxysilanes. The SiMePht-Bu and SiPh3
groups, in which SiMePht-Bu migrates, function as the best
combination to give geminal bis(silyl) aldehyde and enol
derivatives with high diastereoselectivity. The silyl group
migrates with retention of conguration. Enantioselective
generation of the stereogenic carbon center suggests that Si-to-
C chirality transfer is a promising method to construct optically
pure chiral organosilanes. Further applications of this strategy
are being explored in our group.
4
A. Nakazaki, T. Nakai and K. Tomooka, Angew. Chem., Int.
Ed., 2006, 45, 2235.
Conflicts of interest
5
For reviews of enatioselective generation of stereogenic
silicon center, see: (a) M. Oestreich, Synlett, 2007, 1629; (b)
L. W. Xu, L. Li, G. Q. Lai and J. X. Jiang, Chem. Soc. Rev.,
There are no conicts to declare.
2
5
011, 40, 1777; (c) L. W. Xu, Angew. Chem., Int. Ed., 2012,
1, 12932; (d) Y. Wu, L. Gao and Z. L. Song, Chem. Bull.,
Acknowledgements
We are grateful for nancial support from the NSFC (21622202,
2015, 78, 676; (e) R. Shintani, Asian J. Org. Chem., 2015, 4,
510; (f) J. O. Bauer and C. Strohmann, Eur. J. Inorg. Chem.,
21502125).
2016, 2868; (g) Y. M. Cui, Y. Lin and L. W. Xu, Coord.
Chem. Rev., 2017, 330, 37. For selected progresses, see: (h)
K. Igawa, J. Takada, T. Shimono and K. Tomooka, J. Am.
Chem. Soc., 2008, 130, 16132; (i) Y. Yasutomi, H. Suematsu
and T. Katsuki, J. Am. Chem. Soc., 2010, 132, 4510; (j)
R. Shintani, H. Otomo, K. Ota and T. Hayashi, J. Am. Chem.
Soc., 2012, 134, 7305; (k) J. O. Bauer and C. Strohmann,
Angew. Chem., Int. Ed., 2014, 53, 720; (l) R. Shintani,
C. Takagi, T. Ito, M. Naito and K. Nozaki, Angew. Chem.,
Int. Ed., 2015, 54, 1616; (m) R. Shintani, R. Takano and
K. Nozaki, Chem. Sci., 2016, 7, 1205; (n) L. Chen,
J. B. Huang, Z. Xu, Z. J. Zheng, K. F. Yang, Y. M. Cui, J. Cao
and L. W. Xu, RSC Adv., 2016, 6, 67113; (o) K. Igawa,
D. Yoshihiro, Y. Abe and K. Tomooka, Angew. Chem., Int.
Ed., 2016, 55, 5814; (p) Q. W. Zhang, K. An, L. C. Liu,
Q. Zhang, H. F. Guo and W. He, Angew. Chem., Int. Ed.,
2017, 56, 1125; (q) X. F. Bai, J. F. Zou, M. Y. Chen, Z. Xu,
L. Li, Y. M. Cui, Z. J. Zheng and L. W. Xu, Chem.–Asian J.,
2017, 12, 1730; (r) Y. Sato, C. Takagi, R. Shintani and
K. Nozaki, Angew. Chem., Int. Ed., 2017, 56, 9211; (s)
G. Zhan, H. L. Teng, Y. Luo, S. J. Lou, M. Nishiura and
Notes and references
1
(a) J. L. Speier, J. Am. Chem. Soc., 1952, 74, 1003; (b) R. West,
R. Lowe, H. F. Stewart and A. Wright, J. Am. Chem. Soc., 1971,
93, 282.
2
(a) M. Lautens, P. H. M. Delanghe, J. B. Goh and C. H. Zhang,
J. Org. Chem., 1992, 57, 3270; (b) C. Gibson, T. Buck,
M. Noltemeyer and R. Br u¨ ckner, Tetrahedron Lett., 1997,
3
8, 2933; (c) T. N. Mitchell, M. Scht u¨ ze and F. Gießelmann,
Synlett, 1997, 183; (d) J. Bousbaa, F. Ooms and A. Krief,
Tetrahedron Lett., 1997, 38, 762; (e) C. Gibson, T. Buck,
M. Walker and R. Br u¨ ckner, Synlett, 1998, 201; (f)
T. N. Mitchell and M. Sch u¨ tze, Tetrahedron, 1999, 55, 1285;
(
g) B. M. Comanita, S. Woo and A. G. Fallis, Tetrahedron
Lett., 1999, 40, 5283; (h) M. R. Nahm, X. L. Hu,
J. R. Potnick, C. M. Yates, P. S. White and J. S. Johnson,
Angew. Chem., Int. Ed., 2005, 44, 2377; (i) E. N. Onyeozili
and R. E. Maleczka, Tetrahedron Lett., 2006, 47, 6565; (j)
Y. Mori, Y. Futamura and K. Horisaki, Angew. Chem., Int.
Ed., 2008, 47, 1091; (k) J. A. Brekan, D. Chernyak,
26212 | RSC Adv., 2019, 9, 26209–26213
This journal is © The Royal Society of Chemistry 2019