6582
N. Kawai et al. / Tetrahedron Letters 50 (2009) 6580–6583
1) TMSCl, NaI
1) O3 then PPh3
DCM
CH3CN
N
N
N
Boc
Cbz
Cbz
2) NaHMDS
PhCH2PPh3•Cl
2) CbzCl, NaOH
DCM-H2O
THF
63%
2
5
6
49%
Scheme 2. Determination of the absolute configuration of the cyclized product
References and notes
Table 4
Scope of the intramolecular amination
1. (a) Patil, N. T.; Yamamoto, Y. Tetrahedron Lett. 2004, 45, 3101–3103; (b)
Manabe, K.; Kobayashi, S. Org. Lett. 2003, 5, 3241–3244; (c) Saito, T.; Nishimoto,
Y.; Yasuda, M.; Baba, A. J. Org. Chem. 2006, 71, 8516–8522; (d) Onodera, G.;
Imajima, H.; Yamanashi, M.; Nishibayashi, Y.; Hidai, M.; Uemura, S.
Organometallics 2004, 23, 5841–5848; (e) Bandini, M.; Tragni, M. Org. Biomol.
Chem. 2009, 7, 1501–1507.
Entry Substrate
Product
Yield Ratioa
(%)
(S:R)
NHBoc
1
74
95:5
2. Trost, B. M. Science 1991, 254, 1471–1477.
N
Boc
3. For a review of allylic amination: (a) Johannsen, M.; Jørgensen, K. A. Chem. Rev.
1998, 98, 1689–1708; For a recent review of palladium-catalyzed C–N bond
formation from alcohol: (b) Muzart, J. Tetrahedron 2005, 61, 4179–4212; A
review of the palladium-catalyzed activation of allylic alcohols: (c) Tamaru, Y.
Eur. J. Org. Chem. 2005, 2647–2656; Recent examples of the palladium-
catalyzed activation of allylic alcohols: (d) Nishikata, T.; Lipshutz, B. H. Org. Lett.
2009, 11, 2377–2379; (e) Shue, Y.-J.; Yang, S.-C.; Lai, H.-C. Tetrahedron Lett.
2003, 44, 1481–1485; Asymmetric amination: (f) Yamashita, Y.;
Gospalarathnam, A.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129, 7508–7509;
Review of Pd(II)-catalyzed reaction: (g) Zeni, G.; Larock, R. C. Chem. Rev. 2004,
104, 2285–2309; (h) Tietze, L. F.; IIa, H.; Bell, H. P. Chem. Rev. 2004, 104, 3453–
3516.
OH
8
7
NHBoc
2
65
74:26
N
Boc
OH
10
9
4. For other recent examples of direct substitution of allylic alcohol with amine or
amide. Iodine as a catalyst: (a) Wu, W.; Rao, W.; Er, Y. Q.; Loh, K.; Poh, C. Y.;
Chan, P. W. H. Tetrahedron Lett. 2008, 49, 2620–2624; (b) Motokura, K.;
Nakagiri, N.; Mori, K.; Mizugaki, T.; Ebitani, K.; Jitukawa, K.; Kaneda, K. Org. Lett.
2006, 8, 4617–4620; (c) Yadav, J. S.; Subba Reddy, B. V.; Srinivasa Rao, T.;
Krishna, B. B. M.; Narayana Kumar, G. G. K. S. Chem. Lett. 2007, 36, 1472–1473;
(d) Shirakawa, S.; Shimizu, S. Synlett 2008, 1539–1542; (e) Qin, H.; Yamagiwa,
N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2007, 46, 409–413; (f)
Kothandaraman, P.; Foo, S. J.; Chan, P. W. H. J. Org. Chem. 2009, 74, 5947–5952;
(g) Wang, G.-W.; Shen, Y.-B.; Wu, X.-L. Eur. J. Org. Chem. 2008, 4367–4371.
5. (a) Kawai, N.; Lagrange, J.-M.; Ohmi, M.; Uenishi, J. J. Org. Chem. 2006, 71, 4530–
4537; (b) Kawai, N.; Lagrange, J.-M.; Uenishi, J. Eur. J. Org. Chem. 2007, 2808–
2814; (c) Uenishi, J.; Ohmi, M.; Ueda, A. Tetrahedron: Asymmetry 2005, 16,
1299–1303; (d) Uenishi, J.; Vikhe, Y. S.; Kawai, N. Chem. Asian J. 2008, 3, 473–
483; (e) Vikhe, Y. S.; Kawai, N.; Uenishi, J. J. Org. Chem. 2009, 74, 5174–5180.
6. (a) Hosokawa, T.. In Handbook of Organopalladium Chemistry for Organic
Synthesis; Negishi, E.-i., Ed.; John Wiley and Sons: New York, 2002; Vol. 2, pp
2211–2225; (b) Cacchi, S.; Marinelli, F.. In Handbook of Organopalladium
Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; John Wiley and Sons: New
York, 2002; Vol. 2, pp 2227–2243; (c) Hande, S. M.; Kawai, N.; Uenishi, J. J. Org.
Chem. 2009, 74, 244–253; (d) Muzart, J. Eur. J. Org. Chem. 2007, 3077–3089; (e)
Zhang, Z.; Tan, J.; Wang, Z. Org. Lett. 2008, 10, 173–175.
a
Determined by chiral HPLC.
H
N
O
O
Bi
(OTf)3
O
H
(S )
Figure 1. Proposed chelation intermediate.
7. Synthesis of the precursor for intramolecular amination of amino allylic alcohol
1 is shown in the following. The carbamate 12 was prepared from the nitrile
118 by reductive protection with NiCl2 and NaBH4, Boc2O in dioxane. The chiral
alkenyl borate 149 was synthesized by hydroboration of the alkyne 1310
Acknowledgments
derived from ethyl L-(S)-lactate by the conventional method. The Suzuki cross
This work was supported by a Grant-in-Aid for Scientific Re-
search and in part by the 21st COE Program from the Ministry of
Education, Culture, Sports, Science, and Technology, Japan.
coupling with bromobenzene 12 and alkenyl borate 14 took place in the
presence of PdCl2(dppe) and Et3N in dioxane and H2O followed by deprotection
of the silyl group by TBAF in THF giving the alcohol 1 in 75% yield in two steps.
1) 14
NaBH4, NiCl2
then Boc2O
NHBoc
NHBoc
OH
CN
PdCl2(dppf) (5 mol%)
MeOH
RT, 35 min
89%
NaHCO3 / dioxane-H2O
2) TBAF / THF
75%
Br
11
Br
O
12
1
OTBDMS
OTBDMS
pinacolborane
B
cat. DMA, THF
120 °C
O
13
14
77%