PMID- 18578499
OWN - NLM
STAT- MEDLINE
DCOM- 20080926
LR  - 20131121
IS  - 1520-6904 (Electronic)
IS  - 0022-3263 (Linking)
VI  - 73
IP  - 15
DP  - 2008 Aug 1
TI  - Mechanistic studies on the catalytic asymmetric Mannich-type reaction with 
      dihydroisoquinolines and development of oxidative Mannich-type reactions starting 
      from tetrahydroisoquinolines.
PG  - 5859-71
LID - 10.1021/jo800800y [doi]
AB  - Detailed mechanistic studies on our recently reported asymmetric addition 
      reactions of malonates to dihydroisoquinolines (DHIQs) catalyzed by chiral Pd(II) 
      complexes were carried out. It was found that an N,O-acetal was generated in situ 
      by the reaction of DHIQ with (Boc)2O, and cooperative action of the Pd(II) 
      complex as an acid-base catalyst allowed the formation of a chiral Pd enolate and 
      a reactive iminium ion via alpha-fragmentation. The iminium ion was also 
      accessible via oxidation with DDQ as an oxidant, and a catalytic asymmetric 
      oxidative Mannich-type reaction was achieved with tetrahydroisoquinolines (THIQs) 
      as starting materials. This oxidation protocol was applicable to 
      N-acryloyl-protected THIQs, allowing the efficient synthesis of optically active 
      tetrahydrobenzo[a]quinolizidine derivatives via intramolecular Michael reaction.
FAU - Dubs, Christian
AU  - Dubs C
AD  - Synthetic Organic Chemistry Laboratory, RIKEN 2-1 Hirosawa, Wako, Saitama 
      351-0198, Japan.
FAU - Hamashima, Yoshitaka
AU  - Hamashima Y
FAU - Sasamoto, Naoki
AU  - Sasamoto N
FAU - Seidel, Thomas M
AU  - Seidel TM
FAU - Suzuki, Shoko
AU  - Suzuki S
FAU - Hashizume, Daisuke
AU  - Hashizume D
FAU - Sodeoka, Mikiko
AU  - Sodeoka M
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20080626
PL  - United States
TA  - J Org Chem
JT  - The Journal of organic chemistry
JID - 2985193R
RN  - 0 (Amines)
RN  - 0 (Esters)
RN  - 0 (Imines)
RN  - 0 (Isoquinolines)
RN  - 0 (Ligands)
RN  - 0 (Mannich Bases)
RN  - 5TWQ1V240M (Palladium)
SB  - IM
MH  - Amines/chemistry
MH  - Catalysis
MH  - Crystallography, X-Ray
MH  - Esters/chemistry
MH  - Imines/chemistry
MH  - Isoquinolines/*chemistry
MH  - Ligands
MH  - Magnetic Resonance Spectroscopy
MH  - Mannich Bases/chemistry
MH  - Models, Molecular
MH  - Molecular Structure
MH  - Oxidation-Reduction
MH  - Palladium/chemistry
MH  - Spectrophotometry, Infrared
MH  - Stereoisomerism
MH  - Temperature
EDAT- 2008/06/27 09:00
MHDA- 2008/09/27 09:00
CRDT- 2008/06/27 09:00
PHST- 2008/06/27 09:00 [pubmed]
PHST- 2008/09/27 09:00 [medline]
PHST- 2008/06/27 09:00 [entrez]
AID - 10.1021/jo800800y [doi]
PST - ppublish
SO  - J Org Chem. 2008 Aug 1;73(15):5859-71. doi: 10.1021/jo800800y. Epub 2008 Jun 26.