Enantioselective Synthesis of Unnatural (<i>S</i>)-(+)-Cocaine

Lee, Jae Chol; Lee, Kwang-Ho; Kun, Jin

doi:10.1021/jo000348c

Cited by 41 publications

(18 citation statements)

References 10 publications

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“…Tropinone has been successfully used in this capacity for the synthesis of several bioactive derivatives, such as cocaine [16] and its analogues [6,7], as well as of several other alkaloids [17][18][19][20][21]. Recently, we discovered and investigated stereoselective reactions of tropinone and granatanone promoted by water.…”

Section: Introductionmentioning

confidence: 99%

Determination of the N-invertomer stereochemistry in N-substituted nortropanones and norgranatanones using computational and NMR methods

Sidorowicz

Ratkiewicz

Nodzewska

et al. 2015

Comptes Rendus. Chimie

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Section: Introductionmentioning

confidence: 99%

Determination of the N-invertomer stereochemistry in N-substituted nortropanones and norgranatanones using computational and NMR methods

Sidorowicz

Ratkiewicz

Nodzewska

et al. 2015

Comptes Rendus. Chimie

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“…Enantiomerically pure, and racemic, diastereomerically pure aldols of tropinone have been used as key intermediates in stereoselective syntheses of natural tropane alkaloids and their analogues [1], including the unnatural enantiomer of cocaine ( ent -cocaine) [2], knightinol [3], alkaloid KD-B [3] and ferrugine [4–5]. Stereoselective syntheses of nortropinone aldols [6–7] and N-protected nortropinone aldols [5,8–9], which can open access to other N-substituted analogues, have also been described.…”

Section: Introductionmentioning

confidence: 99%

Determination of the relative configuration of tropinone and granatanone aldols by using TBDMS ethers

Łaźny¹,

Nodzewska²,

Sidorowicz³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThe relative configurations of tert-butyldimethylsilyl (TBDMS) ethers of all four diastereomers of the aldols of tropinone (8-methyl-8-azabicyclo[3.2.1]octan-3-one), as well as of granatanone (9-methyl-9-azabicyclo[3.3.1]nonan-3-one), were determined from NMR data, and from the observed interconversion of the diastereomers (exo,anti to endo,syn and exo,syn to endo,anti). The exo forms invert to endo isomers in the presence of silica gel. The relative configuration of a new isomer of tropinone aldol accessible synthetically through the direct solventless reaction of tropinone and benzaldehyde in the presence of water was determined as exo,syn by comparison of NMR data of the aldol isomers, in particular vicinal coupling constants and shifts corresponding to the side-chain CH group, with data of related TBDMS derivatives and confirmed by single-crystal X-ray diffraction.

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“…The mono aldol condensation of cyclic ketones with aryl aldehydes has been achieved in the presence of strong bases, [6,7] and the resulting b-hydoxyketone product can then be easily dehydrated to the corresponding a, b-unsaturated ketone. Thus, we found that when tropinone was lithiated with lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide (LHMDS), the resulting lithium enolate could be condensed with an appropriate aryl aldehyde to afford the corresponding b-hydroxyketone with high regioselectivity, affording mainly the expected exo-anti-isomer (2) (see Sch.…”

Section: Introductionmentioning

confidence: 99%

“…1 H NMR (CDCl 3 ): d 7.53 (s, 1H, C5 5CH), 7.30-7.47 (m, 5H, PhH), 4.31 (d, J ¼ 6.9 Hz, 1H, CH-1),3.54 (t, J ¼ 6.0 Hz, 1H, CH-4), 2.88 (ddd, J ¼ 18 6,. Compound 3a was prepared in 84% yield as a brown oil.…”

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confidence: 99%