Abstract
A new type of N-nucleophile has been developed in Pd-catalyzed
asymmetric allylic amination with monosubstituted allyl substrates,
affording corresponding branched allyl amines in high regio- and
enantioselectivities. Either OMe or Boc group in products can be
removed easily to provide primary amine derivatives with the optical
purity unchanged.
Key words
palladium - allylic amination - catalysis - regioselectivity - enantioselectivity
References
1a Trost BM.
Crawley ML.
Chem. Rev.
2003,
103:
2921
1b Lu Z.
Ma S.
Angew. Chem. Int. Ed.
2008,
47:
258
1c Norsikian S.
Chang C.-W.
Curr. Org. Synth.
2009,
6:
264
2a Trost BM.
Schroeder GM.
J.
Am. Chem. Soc.
1999,
121:
6759
2b Braun M.
Laicher F.
Meier T.
Angew.
Chem. Int. Ed.
2000,
39:
3494
2c Burger EC.
Tunge JA.
Org.
Lett.
2004,
6:
4113
2d Behenna DC.
Stoltz BM.
J.
Am. Chem. Soc.
2004,
126:
15044
2e Braun M.
Meier T.
Angew. Chem. Int. Ed.
2006,
45:
6952
2f Bélanger .
Cantin K.
Messe O.
Tremblay M.
Paquin J.-F.
J. Am. Chem.
Soc.
2007,
129:
1034
3a Yan X.-X.
Liang C.-G.
Zhang Y.
Hong W.
Cao
B.-X.
Dai L.-X.
Hou X.-L.
Angew. Chem. Int. Ed.
2005,
44:
6544
3b Zheng W.-H.
Zheng B.-H.
Zhang Y.
Hou X.-L.
J. Am. Chem. Soc.
2007,
129:
7718
3c Zhang K.
Peng Q.
Hou X.-L.
Wu Y.-D.
Angew. Chem. Int. Ed.
2008,
47:
1741
3d Liu W.
Chen D.
Zhu X.-Z.
Wan
X.-L.
Hou X.-L.
J.
Am. Chem. Soc.
2009,
131:
8734
3e Lei B.-L.
Ding C.-H.
Yang X.-F.
Wan X.-L.
Hou X.-L.
J.
Am. Chem. Soc.
2009,
131:
18250
3f Chen J.-P.
Ding C.-H.
Liu W.
Hou X.-L.
Dai L.-X.
J. Am.
Chem. Soc.
2010,
132:
15493
4a Akermark B.
Akermark G.
Hegedus LS.
Zetterberg K.
J.
Am. Chem. Soc.
1981,
103:
3037
4b Watson IDG.
Yudin AK.
J.
Am. Chem. Soc.
2005,
127:
17516
5a You S.-L.
Zhu X.-Z.
Luo Y.-M.
Hou X.-L.
Dai
L.-X.
J. Am. Chem. Soc.
2001,
123:
7471
5b Zheng WH.
Sun N.
Hou XL.
Org. Lett.
2005,
7:
5151
5c Watson IDG.
Styler SA.
Yudin AK.
J. Am. Chem. Soc.
2004,
126:
5086
5d Dubovyk I.
Watson IDG.
Yudin AK.
J. Am. Chem. Soc.
2007,
129:
14172
5e Johns AM.
Liu Z.
Hartwig JF.
Angew. Chem. Int. Ed.
2007,
46:
7259
6a Miyabe H.
Matsumura A.
Moriyama K.
Takemoto Y.
Org. Lett.
2004,
6:
4631
6b Miyabe H.
Moriyama K.
Takemoto Y.
Chem.
Pharm. Bull.
2011,
59:
714
6c Gärtner M.
Jäkel M.
Achatz M.
Sonnenschein C.
Tverskoy O.
Helmchen G.
Org. Lett.
2011,
13:
2810
7a Fleming I.
Molecular
Orbitals and Organic Chemical Reactions: Reference Edition
John
Wiley and Sons;
UK:
2010.
7b Heaton MM.
J. Am. Chem. Soc.
1978,
100:
2004
8a Fiaud JC.
Malleron JL.
Tetrahedron Lett.
1981,
22:
1399
8b Lloyd-Jones GC.
Stephen SC.
Chem.
Eur. J.
1998,
4:
2539
8c Lloyd-Jones GC.
Stephen SC.
Murray M.
Butts CP.
Vyskočil .
Kočovský P.
Chem. Eur.
J.
2000,
6:
4348
8d Fairlamb IJS.
Lloyd-Jones GC.
Vyskočil .
Kočovský P.
Chem. Eur. J.
2002,
8:
4443
9 Atobe M.
Yamazaki N.
Kibayashi C.
J.
Org. Chem.
2004,
69:
5595
10 Trost BM.
Dong G.
J. Am. Chem. Soc.
2006,
128:
6054
11a Torre O.
Gotor-Fernández V.
Gotor V.
Tetrahedron: Asymmetry
2006,
17:
860
11b Singh OV.
Han H.
Tetrahedron
Lett.
2007,
48:
7094
11c Chandrasekhar S.
Murali RVNS.
Reddy CR.
Tetrahedron Lett.
2009,
50:
5686
12
General Procedure
for the Allylic Amination
3 H5 )Cl]2 (1.8
mg, 0.005 mmol), ligand (R ,R )-L1 (6.4 mg,
0.010 mmol), and CH2 Cl2 (2.0 mL) under Ar
at r.t. The solution was allowed to stir for 5 min before ester 1 (0.2 mmol), MeONHBoc (44 mg, 0.3 mmol),
and K3 PO4 (63 mg, 0.3 mmol) were added. The
reaction was allowed to stir at r.t. and monitored by TLC until
the disappearance of the ester 1 . The reaction
mixture was passed through a short plug of kieselgur eluted with
CH2 Cl2 . The solvent was removed under reduced
pressure. The crude residue [after ¹ H
NMR analysis to check the regioisomeric ratio (3 /4 )] was purified by flash chromatography
(FC) with EtOAc-PE as the eluent (generally, the two regioisomers
could be separated by FC) to afford the compound 3 .
