Dynamics of Catalytic Resolution of 2-Lithio-N-Boc-piperidine by Ligand Exchange

被引：19

作者：

Beng, Timothy K. ^{[1
]}

Tyree, William S. ^{[1
]}

Parker, Trent ^{[1
]}

Su, Chicheung ^{[2
]}

Williard, Paul G. ^{[2
]}

Gawley, Robert E. ^{[1
]}

机构：

[1] Univ Arkansas, Dept Chem & Biochem, Fayetteville, AR 72701 USA

[2] Brown Univ, Dept Chem, Providence, RI 02912 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 40期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

HIGHLY ENANTIOSELECTIVE REACTIONS; ALPHA-SULFONYL CARBANIONS; ASYMMETRIC DEPROTONATION; THERMODYNAMIC RESOLUTION;

D O I：

10.1021/ja307796e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dynamics of the racemization and catalytic and stoichiometric dynamic resolution of 2-lithio-N-Boc-piperidine (7) have been investigated. The kinetic order in tetramethylethylenediamine (TMEDA) for both racemization and resolution of the title compound and the kinetic orders in two resolving ligands have been determined. The catalytic dynamic resolution is second order in TMEDA and 0.5 and 0.265 order in chiral ligands 8 and 10, respectively. The X-ray crystal structure of ligand 10 shows it to be an octamer. Dynamic NMR studies of the resolution process were carried out. Some of the requirements for a successful catalytic dynamic resolution by ligand exchange have been identified.

引用

页码：16845 / 16855

页数：11

共 38 条

[21] Dixon A. J., 2009, ORG SYNTH, VII, P25
[22] Gawley R.E., 2010, TOPICS STEREOCHEMIST, V26
[23] Structural studies of {6Li} 2-lithiopyrrolidines using NMR spectroscopy
Gawley, RE
Klein, R
Ashweek, NJ
Coldham, I
[J]. TETRAHEDRON, 2005, 61 (13) : 3271 - 3280
[24] Hodgson D.M., 2003, ORGANOLITHIUMS ENANT, V5
[25] Hoppe D, 1997, ANGEW CHEM INT EDIT, V36, P2283
[26] Dynamic Thermodynamic Resolution: Advantage by Separation of Equilibration and Resolution
Lee, Won Koo
Park, Yong Sun
Beak, Peter
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (02) : 224 - 234
[27] Solution structure of unstabilized cyclic α-aminoorganolithiums by 13C, 15N, and 6Li NMR spectroscopy
Low, E
Gawley, RE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (39) : 9562 - 9563
[28] Majewski M., 2006, ORGANOMETALLICS COMP, V8a
[29] Catalytic asymmetric deprotonation using a ligand exchange approach
McGrath, MJ
O'Brien, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (47) : 16378 - 16379
[30] An experimental and theoretical study of the asymmetric lithiation of 1,2,3,5,6,7-hexahydro-3a,4a-diazacyclopenta[def]phenanthren-4-one
Metallinos, Costa
Dudding, Travis
Zaifman, Josh
Chaytor, Jennifer L.
Taylor, Nicholas J.
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (03) : 957 - 963

← 1 2 3 4 →