Chiral Version of the Burgess Reagent and its Reactions with Epoxides

Abstract

A chiral auxiliary version of the Burgess reagent was prepared, and its reactions with epoxides were studied. Diastereomeric sulfamidates were converted to both enantiomers of protected trans-amino alcohols with ee of 84-98%.

Key words

chiral Burgess reagent - epoxides - menthol auxiliary group - sulfamidate - trans-amino alcohol derivatives

References and Notes

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3

The following statement appeared in a review by Lamberth (ref. 2b) published in 2000: ‘The compatibility of the Burgess reagent with many functionalities, e.g. halogens, epoxides, alkenes, alkynes, aldehydes, ketones, acetals, esters, secondary amides, makes it an attractive technique for the introduction of C-C double bonds into highly functionalized molecules.’

9

We thank Prof. Travis Dudding (Brock University) for performing transition state optimization calculations (Gaussian 03) for the C ₂ catalysts as well as for the menthol auxiliary. Full details of these calculations will be disclosed in an upcoming full paper.

10

We thank one of the referees for suggesting this explanation.

14

Compound 18: colorless oil; [α]_D ²³ -48.5 (c 0.275, CHCl₃). IR (film): ν = 3448, 3340, 2956, 2926, 2871, 1631, 1548, 1496, 1446, 1372, 1322, 1173, 1097, 986, 954, 917, 863, 815, 759, 700, 661, 609, 541 cm^-1. ¹H NMR (499 MHz, CDCl₃): δ = 7.28-7.46 (m, 5 H), 7.06 (br s, 1 H), 5.76 (br s, 1 H), 5.06 (dt, J = 9.3, 2.2 Hz, 1 H), 4.80 (td, J = 11.0, 4.6 Hz, 1 H), 4.24 (ddd, J = 10.6, 8.8, 2.8 Hz, 1 H), 4.13 (ddd, J = 18.2, 10.3, 9.2 Hz, 1 H), 2.68 (br s, 1 H), 2.08 (d, J = 12.5 Hz, 1 H), 1.83-1.91 (m, 1 H), 1.67 (d, J = 12.1 Hz, 2 H), 1.32-1.51 (m, 2 H), 0.99 (q, J = 11.6 Hz, 1 H), 0.91 (d, J = 5.8 Hz, 3 H), 0.89 (dd, J = 6.8, 1.0 Hz, 3 H), 0.85 (m, 1 H), 0.76 (t, J = 6.5 Hz, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 160.3, 138.5, 129.1, 128.7, 126.5, 79.5, 75.0, 72.1, 47.1, 40.7, 34.1, 31.5, 26.4, 23.3, 22.4, 21.2, 16.8. HRMS: m/z calcd for C₁₉H₃₀N₂O₅S: 398.1875; found: 398.1855.

15

We thank Dr. Ion Ghiviriga (NMR) and Dr. David Powell (mass spectrometry) from the University of Florida for their assistance with the structure assignment of 18. The details of these assignments will be reported in an upcoming full paper.