Catalytic Use of a Soluble OrganoindiumACHTNUTRGNEUNG(III) Species for Allylation and Crotylation of Ketones
References
dium catalysis: T. J. Barker, E. R. Jarvo, Org. Lett.
2009, 11, 1047.
[1] In contrast to ketones, many allylation methods have
been reported for aldehydes. The most recent review
on aldehyde allylation is: S. E. Denmark, J. Fu, Chem.
Rev. 2003, 103, 2763.
[8] a) T. R. Wu, L. Shen, J. M. Chong, Org. Lett. 2004, 6,
2701; b) E. Canales, K. G. Prasad, J. A. Soderquist, J.
Am. Chem. Soc. 2005, 127, 11572; c) S. Lou, P. N. Mo-
quist, S. E. Schaus, J. Am. Chem. Soc. 2006, 128, 12660;
d) D. S. Barnett, P. N. Moquist, S. E. Schaus, Angew.
Chem. 2009, 121, 8835; Angew. Chem. Int. Ed. 2009, 48,
8679.
[9] The most recent review on the use of indium metal and
salts thereof in organic synthesis: J. S. Yadav, A. An-
thony, J. George, B. V. S. Reddy, Eur. J. Org. Chem.
2010, 591.
[10] Lewis acid activation: a) J. W. J. Kennedy, D. G. Hall, J.
Am. Chem. Soc. 2002, 124, 11586; b) recent review:
J. W. J. Kennedy, D. G. Hall, Angew. Chem. 2003, 115,
4880; Angew. Chem. Int. Ed. 2003, 42, 4732; c) M.
Gravel, H. Lachance, X. Lu, D. G. Hall, Synthesis 2004,
1290; d) V. Rauniyar, D. G. Hall, J. Am. Chem. Soc.
2004, 126, 4518.
[2] Selected examples: a) J. Barluenga, A. Diꢁguez, F. Ro-
drꢂguez, F. J. FaÇanꢃs, Angew. Chem. 2005, 117, 128;
Angew. Chem. Int. Ed. 2005, 44, 126; b) S. Hayashi, K.
Hirano, H. Yorimitsu, K. Oshima, Org. Lett. 2005, 7,
3577; c) Y. Takada, S. Hayashi, K. Hirano, H. Yorimit-
su, K. Oshima, Org. Lett. 2006, 8, 2515; d) S. Hayashi,
K. Hirano, H. Yorimitsu, K. Oshima, J. Am. Chem.
Soc. 2006, 128, 2210; e) P. Zhao, C. D. Incarvito, J. F.
Hartwig, J. Am. Chem. Soc. 2006, 128, 9642; f) T.
Ohmura, H. Furukawa, M. Suginome, J. Am. Chem.
Soc. 2006, 128, 13366.
[3] Selected examples: a) V. Nair, C. N. Jayan, S. Ros, Tet-
rahedron 2001, 57, 9453; b) J. G. Lee, K. I. Choi, A. N.
Pae, H. Y. Koh, Y. Kang, Y. S. Cho, J. Chem. Soc.
Perkin Trans. 1 2002, 1314; c) H. Y. Kim, K. I. Choi,
A. N. Pae, H. Y. Koh, J. H. Choi, Y. S. Cho, Synth.
Commun. 2003, 33, 1899; d) V. Nair, S. Ros, C. N.
Jayan, S. Viji, Synthesis 2003, 2542.
[4] Selected examples: a) T. Miyai, K. Inoue, M. Yasuda,
A. Baba, Synlett 1997, 699; b) Y.-C. Teo, J.-D. Goh, T.-
P. Loh, Org. Lett. 2005, 7, 2743; c) J. Lu, M.-L. Hong,
S.-J. Ji, Y.-C. Teo, T.-P. Loh, Chem. Commun. 2005,
4217; d) J. Lu, S.-J. Ji, Y.-C. Teo, T.-P. Loh, Tetrahedron
Lett. 2005, 46, 7435; e) J. Li, S.-J. Ji, Chin. J. Chem.
2006, 24, 1439.
[5] Selected examples: a) H. Hanawa, S. Kii, K. Maruoka,
Adv. Synth. Catal. 2001, 343, 57; b) A. Cunningham, S.
Woodward, Synthesis 2002, 43; c) K. M. Waltz, J. Gave-
nonis, P. J. Walsh, Angew. Chem. 2002, 114, 3849;
Angew. Chem. Int. Ed. 2002, 41, 3697; d) S. Kii, K. Mar-
uoka, Chirality 2003, 15, 68; e) A. Cunningham, V.
Mokal-Parekh, C. Wilson, S. Woodward, Org. Biomol.
Chem. 2004, 2, 741; f) A. J. Wooten, J. G. Kim, P. J.
Walsh, Org. Lett. 2007, 9, 381.
[11] P. V. Ramachandran, D. Pratihar, D. Biswas, Chem.
Commun. 2005, 1988.
[12] a) U. Schneider, S. Kobayashi, Angew. Chem. 2007, 119,
6013; Angew. Chem. Int. Ed. 2007, 46, 5909; b) U.
Schneider, M. Ueno, S. Kobayashi, J. Am. Chem. Soc.
2008, 130, 13824.
[13] Preparation
of
In
G
(hmds)3
as
a
soluble
organoindiumACHTUNGTREG(NNUN III) source: a) H. Bꢄrger, J. Cichon, U.
Goetze, U. Wannagat, H. J. Wismar, J. Organomet.
Chem. 1971, 33, 1; b) M. Veith, S. Hill, V. Huch, Z.
Anorg. Allg. Chem. 2001, 627, 1495.
[14] During the preparation of this manuscript, the use of
InACHTNURTGNEN(UG III)ACHTUGNTREN(NUNG hmds)3 as a pre-catalyst for lactide polymeri-
zation was reported: J.-C. Buffet, J. Okuda, P. L.
Arnold, Inorg. Chem. 2010, 49, 419.
[15] Isomerization of allyl boronate 4 and/or product 5a via
In
was not observed.
[16] Indeed, [In(III)
In(III)ACTHNURTGENNG(U hmds)3 through alcoholysis with tert-butyl alco-
ACHUTGTNERNNUG(III)ACHTUNTGREN(NUNG hmds)3 catalysis, under the present conditions,
A
E
is
accessible
from
R
[6] a) Copper catalysis: S. Yamasaki, K. Fujii, R. Wada, M.
Kanai, M. Shibasaki, J. Am. Chem. Soc. 2002, 124,
6536; b) silver catalysis: M. Wadamoto, H. Yamamoto,
J. Am. Chem. Soc. 2005, 127, 14556; c) metal-free, stoi-
chiometric method: N. Z. Burns, B. M. Hackman, P. Y.
Ng, I. A. Powelson, J. L. Leighton, Angew. Chem. 2006,
118, 3895; Angew. Chem. Int. Ed. 2006, 45, 3811.
[7] a) Copper catalysis: R. Wada, K. Oisaki, M. Kanai, M.
Shibasaki, J. Am. Chem. Soc. 2004, 126, 8910; b) iri-
hol (3 equiv.) in toluene at reflux for 24 h (see ref.[13b]).
It should be noted that the same alcoholysis reaction
using InACTHNURTGNENG(U III)Cl3 does not proceed with complete con-
version, resulting in mixed In
ACHTUNGTREN(NUNG III) compounds (see
ref.[13b]).
[17] A reviewer suggested that an acyclic transition state
may be possible to give a syn-product. We cannot deny
this possibility at this moment.
Adv. Synth. Catal. 2010, 352, 1461 – 1465
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1465