Highly enantioselective catalytic dynamic resolution of N-Boc-2-lithiopiperidine: synthesis of (R)-(+)-N-Boc-pipecolic acid, (S)-(-)-coniine, (S)-(+)-pelletierine, (+)-beta-conhydrine, and (S)-(-)-ropivacaine and formal synthesis of (-)-lasubine II and (+)-cermizine C.
The catalytic dynamic resolution (CDR) of rac-2-lithio-N-Boc-piperidine using chiral ligand 8 or its diastereomer 9 in the presence of TMEDA has led to the highly enantioselective syntheses of both enantiomers of 2-substituted piperidines using a wide range of electrophiles. The CDR has been applied to the synthesis of (R)- and (S)-pipecolic acid derivatives, (+)-beta-conhydrine, (S)-(+)-pelletierine, and (S)-(-)-ropivacaine and the formal synthesis of (-)-lasubine II and (+)-cermizine C.
Beng
Timothy K
TK
Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, USA.
Gawley
Robert E
RE
D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry; D000577:Amides / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis / Q000737:chemistry; D008094:Lithium / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010875:Pipecolic Acids / Q000138:chemical synthesis / Q000737:chemistry; D010880:Piperidines / Q000138:chemical synthesis / Q000737:chemistry*; D011807:Quinolizines / Q000138:chemical synthesis / Q000737:chemistry; D000077212:Ropivacaine; D013237:Stereoisomerism; D013816:Thermodynamics
D000470:Alkaloids; D000577:Amides; D006574:Heterocyclic Compounds, 2-Ring; D009942:Organometallic Compounds; D010875:Pipecolic Acids; D010880:Piperidines; D011807:Quinolizines; C520251:alpha-conhydrine; C518697:cermizine C; C414385:lasubin I; C008195:isopelletierine; C032727:piperidine; D000077212:Ropivacaine; D008094:Lithium; C007112:coniine; C031345:pipecolic acid
Acc Chem Res. 2009 Feb 17;42(2):224-34
19152329
Top Stereochem. 2010 Jan 1;26:93-133
21804654
Org Biomol Chem. 2006 Dec 7;4(23):4285-91
17102873
J Am Chem Soc. 2009 May 27;131(20):6908-9
19405472
J Am Chem Soc. 2002 Mar 6;124(9):1889-96
11866600
J Am Chem Soc. 2010 Jun 2;132(21):7260-1
20462193
Chem Commun (Camb). 2008 Sep 21;(35):4174-6
18802520
J Org Chem. 2010 Mar 19;75(6):1911-6
20155953