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Synlett 2014; 25(6): 809-812
DOI: 10.1055/s-0033-1340824
DOI: 10.1055/s-0033-1340824
letter
Access to Chiral Tertiary α-Hydroxy-β-Ynyl Esters via One-Pot Addition and Kinetic Resolution
Further Information
Publication History
Received: 26 December 2013
Accepted after revision: 22 January 2014
Publication Date:
13 February 2014 (online)
Abstract
Chiral amino alcohol promoted one-pot addition of zinc alkynylides to α-keto esters and kinetic resolution of the resulting tertiary propargylic alcohols was developed. The reaction provided us an alternative approach to access optically active tertiary α-hydroxy-β-ynyl esters with enantiomeric excesses up to 98%.
Key words
alkynylation - propargylic alcohols - tertiary α-hydroxyl esters - kinetic resolution - amino alcoholSupporting Information
- for this article (characterization data and copies of HPLC) is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
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- 10 Typical Procedure for One-Pot Addition and Kinetic Resolution To a solution of 1b (53.4 mg, 0.2 mmol) in THF (3 mL) phenylacetylene (0.33 mL, 3.0 mmol) and ZnMe2 (1 M in toulene, 2 mL, 2.0 mmol) were added. The mixture was stirred at r.t. for 24 h, and methyl phenylglyoxylate (164 mg, 1.0 mmol) in THF (2 mL) was added via syringe. The resulting solution was stirred at r.t. for additional 30 h, quenched with diluted HCl (1 N, 6 mL), and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with PE–EtOAc (20:1, v/v), which afforded (+)-methyl 2-hydroxy-2,4-diphenylbut-3-ynoate as pale yellow oil (104 mg, 0.39 mmol, 39%). [α]D 20 +14.6 (c 1.0, CHCl3). IR (film): 3483 (br), 3061, 2954, 2230, 1739, 1490, 1450, 1255, 1184, 1115, 1099, 1069, 757, 693 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.75 (m, 2 H), 7.58–7.54 (m, 2 H), 7.47–7.33 (m, 6 H), 4.31 (s, 1 H), 3.85 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 172.4, 139.3, 132.0, 129.0, 128.8, 128.4, 128.3, 126.3, 121.9, 87.0, 86.3, 73.2, 54.3. ESI-HRMS: m/z calcd for C17H14O3 [M + Na]+: 289.0835; found: 289.0831. HPLC [Chiralpak AD-H, hexane–i-PrOH (60:40), 1.0 mL/min, 30 °C, 242 nm]: t r (major) = 5.8 min; t r (minor) = 6.8 min, 94% ee.
For recent reviews, see:
For selected recent examples, see:
For recent reviews, see:
For selected recent examples, see:
For catalytic asymmetric addition of alkynes to trifluoropyruvate, see:
Optically active tertiary α-hydroxy acids (esters) are key intermediates of many natural products and medicines, selected examples, see:
For reviews of kinetic resolution, see:
For kinetic resolution of secondary propargylic alcohols, see: