184535-06-6

Upstream product

• 1036404-00-8 C₁₆H₂₃NO₃ 
• 86990-51-4 N-benzyloxycarbonyl-5-hexenylamine 
• 154499-09-9 (E)-8-benzyloxycarbonylamino-3-octen-2-one 
• 505-18-0 2,3,4,5-tetrahydropyridine 
• 110-89-4 piperidine 
• 2858-66-4 (-)-pelletierine 
• 501-53-1 benzyl chloroformate 
• 2858-67-5 1-[(2S)-piperidin-2-yl]acetone 
• 2156-71-0 N-chloropiperidine 
• 2508-29-4 5-hydroxypentylamine 
• 4396-01-4 isopelletierine 
• 1036403-99-2 (R)-2-[(N-benzyloxycarbonyl)piperidin-2-yl]ethanoic acid 
• 542-05-2 acetonedicarboxylic acid 
• 1369774-33-3 (1R,5R)-9-benzyloxycarbonylamino-2-oxo-1-oxabicyclo[3.3.1]nonane 

Downstream Products

• 68681-73-2 (-)-(2S,4S,9aS)-2-hydroxy-4-(3,4-dimethoxyphenyl)-decahydroquinolizidine 
• 221664-11-5 (4S,9aS)-4-(3,4-dimethoxyphenyl)hexahydro-1H-quinolizin-2(6H)-one 
• 1001338-53-9 (4R,9aR)-4-(3,4-dimethoxyphenyl)octahydro-2H-quinolizin-2one 
• 144409-60-9 (4S,9aR)-4-(3,4-dimethoxyphenyl)octahydro-2H-quinolizin-2-one 
• 2858-66-4 (-)-pelletierine 

Relevant academic research and scientific papers

Asymmetric catalyzed intramolecular aza-Michael reaction mediated by quinine-derived primary amines

An intramolecular organocatalytic enantioselective aza-Michael reaction of carbamates, sulfonamides and acetamides to α,β-unsaturated ketones was developed. This process is promoted by 9-amino-9-deoxy-epi-quinine and diphenyl hydrogen phosphate to afford

Asymmetric synthesis of (+)- and (-)-deoxyfebrifugine and deoxyhalofuginone

Both enantiomers of deoxyfebrifugine (4) and deoxyhalofuginone (5), analogues of the quinazolinone-containing biologically active compounds febrifugine (1) and halofuginone (3), have been prepared in a six-step reaction sequence featuring an organocatalyzed Mannich reaction as the key stereo-inducing step. The compounds were isolated as their dihydrobromide salts in 29-42% overall yield and in 74-80% enantiomeric excess.

Strategies for the Asymmetric Construction of Pelletierine and its Use in the Synthesis of Sedridine, Myrtine, and Lasubine

Three methods for the asymmetric synthesis of both enantiomers of pelletierine 6 are reported. Bella's proline-based Mannich process gave (R)- and (S)-Cbz-protected 6 in good yields from Δ1-piperideine 14 and in reasonable enantiomeric excess (74–80 % ee). An intramolecular aza-Michael, cinchona-based, organocatalytic method is also reported. With commercially available 9-amino quinine (24a) and quinidine (24b) catalysts, Cbz-protected α,β-unsaturated ketone 23 also gave (R)- and (S)-Cbz-protected 6 in good yields and enantiomeric excess (90–99 % ee). This material was used to synthesize both optically active forms of deoxyhalofuginone (26), an analogue of febrifugine which is of interest as an anti-fibrotic agent. Finally, a resolution of racemic pelletierine using (R)- and (S)-mandelic acid 27 is reported. This scalable method gave both enantiomers of Cbz- and Boc-protected 6 in excellent enantiomeric excess (≥ 99 %). Both highly enantioenriched forms of 6 (obtained from the resolution study) were used to synthesize several alkaloids. Firstly, (–)-(S)-Cbz-protected pelletierine 17 was used to prepare naturally occurring sedridine (32) and its epimer allosedridine (8). Then the preparation of both enantiomers of the quinolizidine myrtine (33) by an olefination-intramolecular aza-Michael sequence is reported. Finally, the synthesis of the epimeric quinolizidine alkaloids, lasubine I (34) and lasubine II (35), from (+)- and (–)-Boc-protected pelletierine (29) respectively, is discussed.

Syntheses of (-)-pelletierine and (-)-homopipecolic acid

Enantiomeric syntheses of (-)-homopipecolic acid and (-)-pelletierine have been achieved by chiral resolution of tropanol followed by Baeyer-Villiger oxidation. The methodology provides a practical route for the synthesis of optically pure piperidines. The Royal Society of Chemistry 2012.

Asymmetric organocatalytic intramolecular aza-michael addition of enone carbamates: Catalytic enantioselective access to functionalized 2-substituted piperidines

The synthetically useful functionalized 2-substituted piperidines containing a lateral ketone group have been strategically accessed via an organocatalytic enantioselective intramolecular aza-Michael addition of enone carbamates, in which a novel internal substrate combination of the enone moiety as Michael acceptor and the carbamate moiety as Michael donor was revealed in asymmetric bifunctional organocatalysis. This heteroatom conjugate addition, which was realized by using a catalytic chiral Cinchona-based primary-tertiary diamine and an achiral Bronsted acid, mostly proceeded in high yield and good to excellent stereocontrol (up to 99% ee). This reaction provides an alternative catalytic asymmetric method for installing the stereogenic nitrogen-containing carbon center in functionalized 2-substituted piperidines, leading to the development of a straightforward and expeditious synthesis of some naturally occurring bioactive 2-substituted piperidine alkaloids. Copyright

Microwave-assisted organocatalytic enantioselective intramolecular aza-Michael reaction with α,β-unsaturated ketones

An organocatalytic enantioselective intramolecular aza-Michael reaction of carbamates bearing conjugated ketones as Michael acceptors is described. By using 9-amino-9-deoxy-epi-hydroquinine as the catalyst and pentafluoropropionic acid as a co-catalyst, a series of piperidines, pyrrolidines, and the corresponding benzo-fused derivatives (indolines, isoindolines, tetrahydroquinolines, and tetrahydroisoquinolines) can be obtained in excellent yields and enantioselectivities. In addition, the use of microwave irradiation at 60 °C improves the efficiency of the process giving rise to the final products with comparable yields and enantiomeric excesses. Some mechanistic insights are also considered.

Improved protocol for asymmetric, intramolecular heteroatom Michael addition using organocatalysis: Enantioselective syntheses of homoproline, pelletierine, and homopipecolic acid

(Chemical Equation Presented) An improved protocol for the construction of enantioenriched pyrrolidine, indoline, and piperidine rings using an organocatalyzed, intramolecular heteroatom Michael addition is described. Application to the enantioselective synthesis of homoproline, homopipecolic acid, and pelletierine has been accomplished.

A new asymmetric entry to 2-substituted piperidines. A concise synthesis of (+)-coniine, (-)-pelletierine, (+)-δ-coniceine, and (+)-epidihydropinidine

A new asymmetric route to 2-substituted piperidines involving the Sharpless asymmetric dihydroxylation (AD) of 5-hexenylazide 1 and an intramolecular aminocyclization as crucial steps and its application to the asymmetric synthesis of four piperidine alkaloids, (+)-coniine 2, (-)-pelletierine 3, (+)-δ-coniceine 4, aND (+)-epidihydropinidine 5 is presented.