The barrier to enantiomerization and dynamic resolution of N-Boc-2-lithiopiperidine and the effect of TMEDA.
The kinetics of enantiomerization and dynamic thermodynamic resolution (DTR) of N-Boc-2-lithiopiperidine have been measured, revealing significant differences in enthalpy and entropy for these processes and a role for the achiral ligand TMEDA; the racemization and the DTR are catalytic and first order in [TMEDA], and this has implications for asymmetric synthesis with chiral organolithiums.
Coldham
Iain
I
Department of Chemistry, University of Sheffield, Sheffield, UKS3 7HF. i.coldham@sheffield.ac.uk
Leonori
Daniele
D
Beng
Timothy K
TK
Gawley
Robert E
RE
D002384:Catalysis; D005029:Ethylenediamines / Q000737:chemistry*; D007700:Kinetics; D010880:Piperidines / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D005029:Ethylenediamines; D010880:Piperidines; C005798:N,N,N',N'-tetramethylethylenediamine; C032727:piperidine
J Am Chem Soc. 2001 Aug 22;123(33):8039-46
11506560
Chem Commun (Camb). 2008 Sep 21;(35):4174-6
18802520
Chem Commun (Camb). 2007 Nov 21;(43):4534-6
17971980
Acc Chem Res. 2009 Feb 17;42(2):224-34
19152329
Org Lett. 2005 Sep 29;7(20):4459-62
16178558
Org Lett. 2008 Sep 4;10(17):3923-5
18683935
J Org Chem. 2008 Dec 5;73(23):9393-402
18954115
Acc Chem Res. 2000 Oct;33(10):715-27
11041836
J Am Chem Soc. 2009 May 27;131(20):6908-9
19405472
J Am Chem Soc. 2002 Mar 6;124(9):1889-96
11866600
Chem Commun (Camb). 2006 Jun 28;(24):2607-9
16779493
J Org Chem. 2001 Dec 28;66(26):9056-62
11749647
J Org Chem. 2006 Mar 17;71(6):2411-6
16526791
J Am Chem Soc. 2005 Jan 12;127(1):449-57
15631496
J Org Chem. 2005 Mar 18;70(6):2109-19
15760194
Chemistry. 2006 May 15;12(15):4191-7
16526078
J Am Chem Soc. 2006 Aug 23;128(33):10943-51
16910691
J Am Chem Soc. 2004 Apr 28;126(16):5202-6
15099103
Chem Commun (Camb). 2008 Jan 7;(1):97-8
18399412