Stereocontrolled Annulations of Indolo[2,3-a]quinolizidine-Derived Lactams with a Silylated Nazarov Reagent: Access to Allo and Epiallo Yohimbine-Type Derivatives.

@article{Arioli2015StereocontrolledAO,
  title={Stereocontrolled Annulations of Indolo[2,3-a]quinolizidine-Derived Lactams with a Silylated Nazarov Reagent: Access to Allo and Epiallo Yohimbine-Type Derivatives.},
  author={Federica Arioli and Maria P{\'e}rez and Celeste Are and Carolina Estarellas and Francisco Javier Luque and Joan Bosch and Mercedes Amat},
  journal={Chemistry},
  year={2015},
  volume={21 38},
  pages={
          13382-9
        }
}
The facial selectivity of double Michael addition reactions of the silylated Nazarov reagent 4 to unsaturated indolo[2,3-a]quinolizidine lactams 3 has been studied. Pentacyclic 3-H/15-H trans adducts 5 are generated from Nind -unsubstituted lactams, but the corresponding cis isomers 6 are formed when the indole nitrogen has a tert-butyloxycarbonyl (Boc) substituent. This reversal in the facial selectivity of the annulation has been rationalized by means of theoretical calculations, which… 
7 Citations

Figures and Tables from this paper

Origin of the Base‐Dependent Facial Selectivity in Annulation Reactions of Nazarov‐Type Reagents with Unsaturated Indolo[2,3‐a]quinolizidine Lactams
The methyl-substituted Nazarov reagent 4 stereoselectively reacts with Nind-Boc indoloquinolizidine lactams to give the expected H-3/H-15 cis pentacyclic yohimbine-type adducts when using DBU as the
Stereocontrolled Annulations of Indolo[2,3-a]quinolizidine-Derived Lactams with a Silylated Nazarov Reagent: Access to Allo and Epiallo Yohimbine-Type Derivatives.
The facial selectivity of double Michael addition of the silylated Nazarov reagent (II) and title compounds (I) is studied.
A Straightforward Synthesis of Functionalized cis-Perhydroisoquinolin-1-ones
TLDR
Base-catalyzed annulation reactions of 5,6-dihydro-2(1H)-pyridones with Nazarov-type reagents with stereoselectively provides functionalized cis-perhydroisoquinolin-1-ones.
Enantiopure Indolo[2,3-a]quinolizidines: Synthesis and Evaluation as NMDA Receptor Antagonists
TLDR
This compound represents a hit compound for the development of novel NMDA receptor antagonists with potential applications in neurodegenerative disorders associated with overactivation of NMDA receptors.
Total Syntheses of Naucleamides A-C and E, Geissoschizine, Geissoschizol, (E)-Isositsirikine, and 16-epi-(E)-Isositsirikine.
A divergent approach for the enantioselective total synthesis of eight monoterpenoid indole alkaloids was developed. The approach allows the first total syntheses of naucleamides A-C and E in only
Pyridones – Powerful Precursors for the Synthesis of Alkaloids, Their Derivatives, and Alkaloid-Inspired Compounds
2-Pyridone is characterized by a very wide range of reactivity of a different nature, ranging from electrophilic aromatic substitution, CH–metal-mediated reactions, and NH/OH functionalization of

References

SHOWING 1-10 OF 58 REFERENCES
Enantioselective formal synthesis of (+)-dihydrocorynantheine and (-)-dihydrocorynantheol.
The enantioselective construction of the 3-ethylindolo[2,3-a]quinolizidine moiety present in numerous indole alkaloids is reported, the key steps being a stereoselective cyclocondensation of
Enantio- and Diastereomerically Pure Decalins by Deslongchamps-Type Annulation of Dienolates Containing a Chiral Lactone Substituent
A conceptionally novel 1,3-asymmetric induction has been established. It controls the relative and absolute configuration of up to 5 stereocenters. They emerge from the anionic Diels–Alder reactions
A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)
A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N
Conjugate additions of sulfur-stabilized anions to unsaturated lactams. Synthesis of polyfunctionalized benzo[a]quinolizinone systems.
TLDR
The polyfunctionalized hexahydrobenzo[a]quinolizinone systems obtained could be further elaborated toward emetine-like structures.
The stereoselectivity of michael additions leading to enantiomerically pure indoloquinolizidones
Acylation of the carboline derivatives 6 and 9 with diketene affords the corresponding N-(acetoacetyl)carbolines 7 and 10, respectively. While 10 can be converted into a 1:2.1 mixture of the title
Stereoselective synthesis of cis-decalins via Diels–Alder and double Michael addition of substituted Nazarov reagents
The base-catalyzed cycloaddition and double Michael cyclization of substituted Nazarov reagents and of 1-phenylsulfinyl analogs, with 2-carbomethoxy-2-cyclohexen-1-one 1 yielding cis-decalins is
...
...