Lipase-mediated deracemization of secondary 1-phenyl-substituted propargylic alcohols of different topology

Vlasyuk, A. L.; Gamalevich, G. D.; Игнатенко, А. В.; Serebryakov, É. P.; Стручкова, Марина И.

doi:10.1023/b:rucb.0000035659.02761.1a

Cited by 5 publications

(3 citation statements)

References 15 publications

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“…Enantioenriched ester 41 (Figure B), generated earlier in eight steps via a lipase-catalyzed kinetic resolution of a racemic alcohol, has served as an intermediate in a synthesis of ( R )-4-dodecanolide, which is part of a defensive secretion of rove beetle Bledius mandibullaris . Using our catalytic enantioselective four-component coupling, we can produce ester 41 in one step and 90% ee from commercially available building blocks.…”

Section: Resultsmentioning

confidence: 99%

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols

Yang

2020

J. Am. Chem. Soc.

108

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The yields have not been optimized.General Procedure 1 (GP-1): Preparation of the electrophile. 2 An oven-dried 100 mL round-bottom flask was charged with a magnetic stir bar and either ZnCl2 or ZnBr2 (0.050 equiv), and then it was sealed with a rubber septum cap. The flask was placed under a nitrogen atmosphere by evacuating and backfilling the flask (three cycles), followed by the addition of DCM and the acyl bromide (1.2 equiv). The resulting solution was cooled to -10 °C, and the mixture was stirred for 10 min. At this temperature, the aldehyde (1.0 equiv) was added via syringe pump over 30 min, and the resulting mixture was stirred for 2 h. Then, the reaction mixture was filtered through a short column of neutral aluminium oxide, with a DCM washing. The filtrate was concentrated under reduced pressure. The residue was either purified by vacuum distillation to afford the pure product, or used directly after the determination of its purity by 1 H NMR (CH2Br2 as the internal standard).1-Bromoethyl benzoate. The title compound was synthesized according to GP-1 from ZnCl2 (544 mg, 4.0 mmol), BzBr (11.3 mL, 96.0 mmol), acetaldehyde (4.5 mL, 80 mmol), and DCM (10 mL). The product was purified by vacuum distillation (b.p. = 75-79 °C, 1.2 Torr). 9.6 g (42.1 mmol, 53% yield). Colorless oil. 1 H NMR (400 MHz, CDCl3) δ 8.12 -8.04 (m, 2H), 7.65 -7.56 (m, 1H), 7.52 -7.42 (m, 2H), 6.97 (q, J = 5.9 Hz, 1H), 2.14 (d, J = 5.9 Hz, 3H). cm -1 .1-Bromopropyl benzoate. The title compound was synthesized according to GP-1 from ZnCl2 (870 mg, 6.4 mmol), BzBr (18.0 mL, 154 mmol), propionaldehyde (9.2 mL, 128 mmol), and DCM (20 mL). The product was purified by vacuum distillation (b.p. = 88-90 °C, 0.5 Torr). 22.4 g (92.6 mmol, 72% yield). Colorless oil. ZnCl 2 or ZnBr 2 DCM, -10 °C R O Br Br R 1 O R 1 O H R O S-4 1 H NMR (500 MHz, CDCl3) δ 8.10 -8.05 (m, 2H), 7.65 -7.58 (m, 1H), 7.50 -7.43 (m, 2H), 6.85 (t, J = 5.7 Hz, 1H), 2.36 -2.23 (m, 2H), 1.15 (t, J = 7.3 Hz, 3H). , 961, 908, 716 cm -1 . 1-Bromopentyl benzoate. The title compound was synthesized according to GP-1 from ZnCl2 (544 mg, 4.0 mmol), BzBr (11.3 mL, 96.0 mmol), valeraldehyde (8.5 mL, 80 mmol), and DCM (10 mL). The product was purified by vacuum distillation (b.p. = 103-108 °C, 0.7 Torr). 8.4 g (31.1 mmol, 39% yield). Yellow oil. 1 H NMR (400 MHz, CDCl3) δ 8.10 -8.04 (m, 2H), 7.66 -7.57 (m, 1H), 7.52 -7.44 (m, 2H), 6.89 (t, J = 5.9 Hz, 1H), 2.37 -2.21 (m, 2H), 1.61 -1.49 (m, 2H), 1.48 -1.35 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H). cm -1 .1-Bromo-3-methylbutyl benzoate. The title compound was synthesized according to GP-1 from ZnBr2 (888 mg, 4.0 mmol), BzBr (11.3 mL, 96.0 mmol), isovaleraldehyde (8.6 mL, 80 mmol), and DCM (10 mL). The product was purified by vacuum distillation (b.p. = 95-98 °C, 0.7 Torr). 14.3 g (53.0 mmol, 66% yield). Colorless oil. 1 H NMR (400 MHz, CDCl3) δ 8.12 -8.04 (m, 2H), 7.65 -7.57 (m, 1H), 7.53 -7.42 (m, 2H), 6.95 (dd, J = 7.6, 5.6 Hz, 1H), 2.28 (ddd, J = 14.2, 7.6, 6.6 Hz, 1H), 2.16 (ddd, J = 14.3, 7.3, 5.6 Hz, 1H), 1.99 -1.86 (m, 1H), 0.99 (d, J = ...

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Section: Resultsmentioning

confidence: 99%

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols

Yang

2020

J. Am. Chem. Soc.

108

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“…HRMS (ESI) calcd for C 15 H 22 NO 2 [M + NH 4 ] + , 248.1645; found, 248.1650. 1d is a known compound …”

Section: Methodsmentioning

confidence: 99%

“…1d is a known compound. 23 1-(4-Methoxyphenyl)hept-1-yn-3-yl Methyl Carbonate (1e). Column chromatography on silica gel (eluent: petroleum ether/ethyl acetate, 20:1) afforded the title product as a yellow liquid in 91% (5 mmol scale, 1.257 g) isolated yield over two steps.…”

Section: ■ Conclusionmentioning

confidence: 99%

Gold-Catalyzed Oxidative Reactions of Propargylic Carbonates Involving 1,2-Carbonate Migration: Stereoselective Synthesis of Functionalized Alkenes

2014

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A gold-catalyzed oxidative reaction of propargylic carbonates or acetates using 3,5-dichloropyridine as the oxidant has been developed. The reaction provides efficient access to α-functionalized-α,β-unsaturated ketones with excellent regio- and diastereocontrol via a regioselective attack of the N-oxide to the gold-activated alkyne followed by a 1,2-carbonate migration. In addition, the alkene products could be further transformed into the valuable 5-hydroxycyclopent-2-enones via cyclocondensation with acetone or cyclodimerization under basic conditions.

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Lipase‐Mediated Deracemization of Secondary 1‐Phenyl‐Substituted Propargylic Alcohols of Different Topology.

et al. 2004

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Biochemical syntheses O 0035Lipase-Mediated Deracemization of Secondary 1-Phenyl-Substituted Propargylic Alcohols of Different Topology. -The kinetic enzymatic resolution of secondary propargylic alcohols is studied on three structurally different alcohols (I), (VI) and (VII). Only alcohol (I) gives noticeable conversion in the enzyme-catalyzed acetylation, while the other two alcohols (VI) and (VII) are unreactive due to the unfavorable steric environment of the hydroxy group. The enantioselectivity in enzymatic acetylation of (I) as well as deacetylation of the corresponding racemic acetate (III) is only low (15-20% e.e.). Higher enantioselectivity, however, is achieved by use of the tricarbonylchromium-complexed analogue (IV) (95% e.e.), although the conversion is only low. -(VLASYUK, A. L.; GAMALEVICH, G. D.; IGNATENKO, A. V.; SEREBRYAKOV*, E. P.; STRUCHKOVA, M. I.; Russ.

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Lipase-mediated deracemization of secondary 1-phenyl-substituted propargylic alcohols of different topology

Cited by 5 publications

References 15 publications

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols

Gold-Catalyzed Oxidative Reactions of Propargylic Carbonates Involving 1,2-Carbonate Migration: Stereoselective Synthesis of Functionalized Alkenes

Lipase‐Mediated Deracemization of Secondary 1‐Phenyl‐Substituted Propargylic Alcohols of Different Topology.

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