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Synlett 2011(15): 2262-2264  
DOI: 10.1055/s-0030-1261187
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Regio- and Enantioselective Pd-Catalyzed Allylic Amination of Monosubsti­tuted Allylic Substrates with BocNHOMe

Bao-Hui Zhenga, Chang-Hua Dinga, Xue-Long Hou*a,b
a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China
b Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)54925100; e-Mail: xlhou@sioc.ac.cn;
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Publication History

Received 17 May 2011
Publication Date:
12 August 2011 (online)

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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

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12

General Procedure for the Allylic Amination
To a flame-dried Schlenk tube were added [Pd(C3H5)Cl]2 (1.8 mg, 0.005 mmol), ligand (R,R)-L1 (6.4 mg, 0.010 mmol), and CH2Cl2 (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 K3PO4 (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 CH2Cl2. The solvent was removed under reduced pressure. The crude residue [after ¹H 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.