Synthesis of 2-hydroxymethyl-1-oxaquinolizidine

Börjesson, Lena; Welch, Christopher J.

doi:10.1016/s0040-4020(01)88223-5

Cited by 32 publications

(16 citation statements)

References 13 publications

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“…Pyridincarboxaldehyde was distilled in vacuum prior to use; p-tolyl 2- O -methyl-1-thio- β -D-galactopyranoside ( 14 ),[33] 2-chloro-4-nitrophenyl β -D-mannopyranoside ( 11b ),[28] 2-chloro-4-nitrophenyl β -D-galactopyranoside ( 11d ), [26] N , N ′-[1,4-bis[(pyridin-2-ylmethyl)amino]propan-2-ol]ato dicopper(II) (μ-acetato) diperchlorate, Cu 2 bpdpo ( 1 ),[7] and ( S )-methyl malate, ( S -5 )[40–42] were prepared as described; all other chemicals were used as received from commercial suppliers.…”

Section: Methodsmentioning

confidence: 99%

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

Striegler

Fan

Rath

2016

Journal of Catalysis

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Two chiral binuclear copper(II) complexes were synthesized and characterized for the first time as efficient chemoselective catalysts for the hydrolysis of aryl glycosides and disaccharides in aqueous solution at near neutral pH. Under these conditions, discrimination of epimeric aryl α-glycopyranosides was observed both by 29-fold different reaction rates and 3-fold different proficiency of the catalyst. Additionally, large differentiation of the nature of α- and β- glycosidic bond in aryl glycosides as model compounds is apparent, but also noted in selected disaccharides. The influence of the chirality of the complexes and the role of the configuration of the carbohydrate upon interaction with the catalyst is discussed in detail. Lastly, a putative mechanism for the metal complex-catalyzed hydrolysis is derived from the experimental evidence pointing at deprotonation of the hydroxyl group at C-2 as a pre-requisite for glycoside hydrolysis.

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Section: Methodsmentioning

confidence: 99%

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

Striegler

Fan

Rath

2016

Journal of Catalysis

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“…For related synthetic procedures, see: Borjesson & Welch (1992); Dardonville & Gilbert (2003); Gaunt et al (2003); Saito et al (1992); You et al (2006).…”

Section: Related Literaturementioning

confidence: 99%

“…So it is a useful intermediate for synthesis of the fluorinecontaining analogues of natural product with potential bioactivity. The title compound was prepared from L-malic acid according to the method developed by our group (You et al, 2006) and other groups (Borjesson et al, 1992;Dardonville et al, 2003;Gaunt et al, 2003;Saito et al, 1992). Our interest is focused on the changes caused by introducing difluoromethylene group into the lactone ring.…”

Section: Data Collectionmentioning

confidence: 99%

(S)-6-{[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]methyl}-5,5-difluoro-5,6-dihydro-2H-pyran-2-one

et al. 2009

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“…Found: C,59.63;H,6.83;N,9. 1.1 CHCl 3 ); IR (film) 3028,2962,2875,1758,1497,1455,1397,1366,1222,1098, 1029 cm -1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 7.31 (dd, J = 7.6,7.6 Hz,2H),7.24 (dd,J = 7.6,7.6 Hz,1H),7.16 (d,J = 7.2 Hz,2H),1H),2H),1H),3.44 (dd,J = 13.6,3.4 Hz,1H),3.29 (ddd,J = 8.3,8.3,8.3 Hz,1H),1H),2.52 (dd,J = 13.3,10.4 Hz,1H), 2.08-2.01 (m, 1H), 1.95-1.87 (m, 1H), 1.83-1.72 (m, 2H), 1.43-1.36 (m, 1H), 1.28-1.19 (m, 1H), 0.91 (dd, J = 7.5, 7.5 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 156. 2,136.2,128.8 (2C),126.9,67.4,61.7,57.9,48.6,39.5,28.4,27.1,21.5,10.5;MS (CI)…”

Section: S9mentioning

confidence: 99%

Mn-Mediated Coupling of Alkyl Iodides and Chiral N-Acylhydrazones: Optimization, Scope, and Evidence for a Radical Mechanism

et al. 2006

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Stereoselective radical additions have excellent potential as mild, nonbasic carbon-carbon bond constructions for direct asymmetric amine synthesis. Efficient intermolecular radical addition to C=N bonds with acyclic stereocontrol has previously been limited mainly to secondary and tertiary radicals, a serious limitation from the perspective of synthetic applications. Here, we provide full details of the use of photolysis with manganese carbonyl to mediate stereoselective intermolecular radical addition to N-acylhydrazones. Photolysis (300 nm) of alkyl halides and hydrazones in the presence of Mn2(CO)10 and InCl(3) as a Lewis acid led to reductive radical addition; diastereomer ratios ranged from 93:7 to 98:2 at ca. 35 degrees C. The reaction tolerates additional functionality in either reactant, enabling subsequent transformations as shown in an efficient asymmetric synthesis of coniine. A series of hydrazones bearing different substituents on the oxazolidinone auxiliary were compared; consistently high diastereocontrol revealed that the identity of the substituent had little practical effect on the diastereoselectivity. Further mechanistic control experiments confirmed the intermediacy of radicals and showed that independently prepared alkyl- or acylmanganese pentacarbonyl compounds do not undergo efficient addition to the N-acylhydrazones under thermal or photolytic (300 nm) conditions. These Mn-mediated conditions avoid toxic tin reagents and enable stereoselective intermolecular radical additions to C=N bonds with the broadest range of alkyl halides yet reported, including previously ineffective primary alkyl halides.

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Synthesis of 2-hydroxymethyl-1-oxaquinolizidine

Cited by 32 publications

References 13 publications

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

(S)-6-{[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]methyl}-5,5-difluoro-5,6-dihydro-2H-pyran-2-one

Mn-Mediated Coupling of Alkyl Iodides and Chiral N-Acylhydrazones: Optimization, Scope, and Evidence for a Radical Mechanism

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