Enantiopure N-Boc piperidine-2-ethanol for the synthesis of (+)- and (−)-dumetorine, and (+)- and (−)-epidihydropinidine

Passarella, Daniele; Riva, Sergio; Grieco, Gabriele; Cavallo, Francesco; Checa, Begoña; Arioli, Federica; Riva, Elena; Comi, D.; Danieli, Bruno

doi:10.1016/j.tetasy.2008.12.008

Cited by 14 publications

(13 citation statements)

References 43 publications

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“…Starting from ( R )- N -Boc-2-piperidine ethanol, Passarella et al synthesized (2 R ,6 S )- 19 in five steps and used it to prepare both enantiomers of epidihydropinine. 20 Highly regioselective Wacker oxidation 21 of trans - 19 afforded the pelletierine derivative 20 in 92% yield.…”

Section: Resultsmentioning

confidence: 99%

“…Data for the trans isomer; [α] D 22 +20.3 ( c = 1.5, CHCl 3 ), lit. 20 [α] D 25 +23.7 ( c = 1.5, CHCl 3 ). All other data as reported.…”

Section: Methodsmentioning

confidence: 99%

“…All other data as reported. 20 The er was evaluated by CSP-GC-MS on a β-cyclodextrin-permethylated 120 fused silica capillary column [30 m × 0.25 mm i.d., 20% permethylated β-cyclodextrin in SPB-35 poly(35% diphenyl/65% dimethyl)siloxane, initial temperature = 100 °C, final temperature = 200 °C, hold time = 10 min, rate = 5 °C/min.…”

Section: Methodsmentioning

confidence: 99%

“…The combined organic layers were washed with brine, dried over MgSO 4 and concentrated under reduced pressure to give 50 mg of (−)-epidihydropinidine in 100% yield, [α] D 22 −2.2 ( c 0.25, CHCl 3 ), lit. 20 for enantiopure (−)-epidihydropinidine [α] D 25 −2.7 ( c 0.2, CHCl 3 ).…”

Section: Methodsmentioning

confidence: 99%

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Catalytic Dynamic Resolution Applied to the Synthesis of 2,6-Disubstituted Piperidines: Preparation of (+)-Lupetidine and (–)-Epidihydropinidine

Beng¹,

Gawley²

2012

HETEROCYCLES

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Section: Resultsmentioning

confidence: 99%

“…Data for the trans isomer; [α] D 22 +20.3 ( c = 1.5, CHCl 3 ), lit. 20 [α] D 25 +23.7 ( c = 1.5, CHCl 3 ). All other data as reported.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Catalytic Dynamic Resolution Applied to the Synthesis of 2,6-Disubstituted Piperidines: Preparation of (+)-Lupetidine and (–)-Epidihydropinidine

Beng¹,

Gawley²

2012

HETEROCYCLES

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“…3 Additionally, the versatility of substituted pyrrolidines and piperidines in the synthesis has been amply demonstrated. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] In 1989, Beak disclosed that unsubstituted Boc-protected azaheterocycles may be effectively functionalized at the a-position through a lithiation/alkylation sequence. 19 Several researchers, [20][21][22][23][24][25][26] including one of us, 27,16 have since extended the Beak methodology to include sequential a-functionalizations en route to access a,a-and a,a 0 -disubstituted N-heterocycles, in both racemic and enantioenriched forms.…”

mentioning

confidence: 99%

Diastereoselective synthesis of α,α,α′-trisubstituted pyrrolidines and piperidines by directed sequential lithiation/alkylation

Beng

Fox

2015

Tetrahedron Letters

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Asymmetric Substitutions of 2‐Lithiated N‐Boc‐piperidine and N‐Boc‐azepine by Dynamic Resolution

Coldham

Raimbault

Whittaker

et al. 2010

Chemistry A European J

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Proton abstraction of N-tert-butoxycarbonyl-piperidine (N-Boc-piperidine) with sBuLi and TMEDA provides a racemic organolithium that can be resolved using a chiral ligand. The enantiomeric organolithiums can interconvert so that a dynamic resolution occurs. Two mechanisms for promoting enantioselectivity in the products are possible. Slow addition of an electrophile such as trimethylsilyl chloride allows dynamic resolution under kinetic control (DKR). This process occurs with high enantioselectivity and is successful by catalysis with substoichiometric chiral ligand (catalytic dynamic kinetic resolution). Alternatively, the two enantiomers of this organolithium can be resolved under thermodynamic control with good enantioselectivity (dynamic thermodynamic resolution, DTR). The best ligands found are based on chiral diamino-alkoxides. Using DTR, a variety of electrophiles can be used to provide an asymmetric synthesis of enantiomerically enriched 2-substituted piperidines, including (after Boc deprotection) the alkaloid (+)-beta-conhydrine. The chemistry was extended, albeit with lower yields, to the corresponding 2-substituted seven-membered azepine ring derivatives.

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Enantiopure N-Boc piperidine-2-ethanol for the synthesis of (+)- and (−)-dumetorine, and (+)- and (−)-epidihydropinidine

Cited by 14 publications

References 43 publications

Catalytic Dynamic Resolution Applied to the Synthesis of 2,6-Disubstituted Piperidines: Preparation of (+)-Lupetidine and (–)-Epidihydropinidine

Catalytic Dynamic Resolution Applied to the Synthesis of 2,6-Disubstituted Piperidines: Preparation of (+)-Lupetidine and (–)-Epidihydropinidine

Diastereoselective synthesis of α,α,α′-trisubstituted pyrrolidines and piperidines by directed sequential lithiation/alkylation

Asymmetric Substitutions of 2‐Lithiated N‐Boc‐piperidine and N‐Boc‐azepine by Dynamic Resolution

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