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ChemComm
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DOI: 10.1039/C5CC05459A
COMMUNICATION
Journal Name
Eur. J., 2000,
6
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very special for this nitrosocarbonyl aldol cascade, which is in
agreement with our prior intuition.
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Int. Ed., 2011, 50, 5630; (b) M. Baidya and H. Yamamoto,
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Further tuning the reaction conditions revealed that the
conversion of the intermediate 3b’ to 3b is comparatively slow
for 2-ethyl-2-oxazoline (EtOx) ligand in THF solvent and a 3:1
mixture of 3b’ and 3b was isolated by shorting the reaction
time to 4.5 h (Scheme 4, ESI page S18). When this mixture was
exposed to pure CH3CN under nitrogen and oxygen separately,
3b’ slowly converted to 3b in 20 h at room temperature for
both the cases. Under our optimized reaction conditions, this
conversion took place only in 5 h. Such disparity in reaction
rates suggests that the conversation of 3b’ to 3b is thermally
feasible, however, the copper-pyridine complex catalyzes this
novel transformation.
3
4
6, 1; (e) W. Adam and O. Krebs, Chem.
2
5
6
slow
OSi(Me)2TMS
6,
CH3CN, N2 or O2
20 h
SiMe2TMS
MeO
O
O
N
O
CuCl (20 mol%)
EtOx (10 mol%)
H
1b
+
N
Cbz
Cbz
+
O2 Balloon, THF,
MeO
MeO
O
rt, 4.5 h
3b'
(3:1)
3b
BnO
NHOH
CuCl (20 mol%)
pyridine (10 mol%),
2a
5 h
O2, CH3CN
7
Amination with nitrosobenzenes: (a) N. Momiyama and H.
Yamamoto, J. Am. Chem. Soc., 2004, 126, 5360; (b) N.
Scheme 4 Mechanistic insights.
Momiyama and H. Yamamoto, J. Am. Chem. Soc., 2005, 127
,
1080; (c) T. Kano, M. Ueda, J. Takai and K. Maruoka, J. Am.
Chem. Soc., 2006, 128, 6046; (d) J. L. Cantarero, M. B. Cid, T.
B. Poulsen, M. Bella, J. L. G. Ruana and K. A. Jørgensen, J.
Org. Chem., 2007, 72, 7062; (e) C. Palomo, S. Vera, I. Velilla,
In conclusion, we have developed unprecedented
Mukaiyama aldol reaction of in situ generated nitrosocarbonyl
compounds with silyl enol ethers having disilane backbone.
A. Mielgo and E. G. Bengoa, Angew. Chem. Int. Ed., 2007, 46
,
The reaction is perfect N-selective and delivered
α-amino
8054; (f) T. Sasaki, Y. Ishibashi and M. Ohno, Chem. Lett.,
1983, 863; (g) T. Sasaki, K. Mori and M. Ohno, Synthesis,
1985, 279.
For O-nitroso aldol reactions: (a) M. Baidya, K. A. Griffin and
H. Yamamoto, J. Am. Chem. Soc., 2012, 134, 18566; (b) C. P.
Frazier, D. Sandoval, L. I. Palmer and J. Read de Alaniz, Chem.
ketones in excellent yields with concomitant N–O bond
cleavage. Such unique cascade of C–N bond formation and N–
O bond cleavage in a single step had not been realized
previously in the field of nitrosocarbonyl chemistry. The
8
9
reaction is scalable and
a high diastereoselectivity was
Sci., 2013, 4, 3857; (c) B. Maji and H. Yamamoto, Angew.
observed when chiral nitrosocompound was employed.
Studies towards a catalytic asymmetric variant of this novel
transformation and computational studies to disclose the
mechanistic details are currently ongoing.
Chem. Int. Ed., 2014, 53, 14472; (d) W. Yang, L. Huang, Y. Yu,
D. Pflästerer, F. Rominger and A. S. K. Hashmi, Chem. Eur. J.,
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Reactions with β-ketoesters: (a) D. Sandoval, C. P. Frazier, A.
Bugarin and J. Read de Alaniz, J. Am. Chem. Soc., 2012, 134
We gratefully acknowledge IITM for financial support (seed
grant). I.R. and H.K. thank IITM for HTRA. G.S.G. thanks UGC,
New Delhi for a JRF.
,
18948; (b) C. Xu, L. Zhang and S. Luo, Angew. Chem. Int. Ed.,
2014, 53, 4149; (c) B. Maji, M. Baidya and H. Yamamoto,
Chem. Sci., 2014,
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C. Xu, X. Mi and S. Luo, Chem. Asian J., 2014, , 3565.
5, 3941; (d) M.–Q. Liang and C.-D. Lu,
9
Notes and references
10 Reactions with aldehydes: a) T. Kano, F. Shirozu and K.
Maruoka, J. Am. Chem. Soc., 2013, 135, 18036; (b) T. Kano, F.
Shirozu and K. Maruoka, Org. Lett., 2014, 16, 1530; (c) B.
1
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,
11 S. Murru, C. S. Lott, F. R. Fronczek and R. S. Srivastava, Org.
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12 R. T. Sanderson, in Chemical Bonds and Bond Energy,
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13 For the rearrangement of organosilicon compounds: A. G.
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14 Reaction did not work with corresponding silyl enol ethers
derived from cyclohexanone and cyclopentanone.
2
For reviews: (a) J. M. Janey, Angew. Chem. Int. Ed., 2005, 44,
4292; (b) T. Vilaivan and W. Bhanthumnavin, Molecules,
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4 | J. Name., 2012, 00, 1-3
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