Next Article in Journal
Amburana cearensis: Pharmacological and Neuroprotective Effects of Its Compounds
Next Article in Special Issue
New Advances in the Synthetic Application of Enantiomeric 1-Phenylethylamine (α-PEA): Privileged Chiral Inducer and Auxiliary
Previous Article in Journal
Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 25
Issue 15
10.3390/molecules25153392
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity

by
Bogdan Bujnicki
1,
Jarosław Błaszczyk
1,*,
Marek Chmielewski
2 and
Józef Drabowicz
1,3,*
1
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Division of Organic Chemistry, Sienkiewicza 112, 90–363 Łódź, Poland
2
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01–224 Warszawa, Poland
3
Institute of Chemistry, Jan Długosz University, Aleja Armii Krajowej 13/15, 42–200 Częstochowa, Poland
*
Authors to whom correspondence should be addressed.
Molecules 2020, 25(15), 3392; https://doi.org/10.3390/molecules25153392
Submission received: 1 July 2020 / Revised: 22 July 2020 / Accepted: 23 July 2020 / Published: 27 July 2020
(This article belongs to the Special Issue Advances in Enantioselective Syntheses and Chiral Separations)
Browse Figures
Review Reports Versions Notes

Abstract

:
The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P212121, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.

Graphical Abstract

1. Introduction

Racemic and optically active diastereoisomeric and/or enantiomeric sulfinic esters played a very important role in the development of sulfur chemistry and especially sulfur stereochemistry [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15]. Preparation of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a by reacting p-toluenesulfinyl chloride 1a with (-)-(1R,3S,5R)-menthol in the presence of pyridine (Scheme 1) [16], confirmed for the first time stereogenity of a sulfinyl sulfur atom and its optical stability at room temperature [2,3]. It is worth noting that very recently diasteroisomerically pure sulfinate 3a was isolated in almost quantitative yield by reacting p-toluenesulfinyl chloride 1a with (-)-(1R,3S,5R)-menthol in the absence of a base as an HCl scavenger [17], while all attempts of its isolation under flow conditions resulted in the formation of 2a/3a mixtures [18].
This sulfinate was used as a precursor of the first enantiomerically pure sulfoxide, i.e., ethyl p-tolyl sulfoxide [19,20,21]. Subsequently, the reaction of this diastereoisomeric sulfinates with organometallic reagents has been commonly applied to obtain a very rich family of enantiomerically pure sulfoxides and other sulfinyl derivatives as “Andersen synthesis” [1,2,3,4,5,6,7,8]. Following sulfinylation of the hydroxyl groups of a sugar moiety was used to prepare other diastereomeric sulfinates, which are used again as substrates for the synthesis of enantiomerically pure sulfinyl derivatives. The best results were obtained with diacetone α-d-glucose (DAG) and its cyclohexyl analogue, dicyclohexylidene α-d-glucose (DCG) (Scheme 2) [22,23,24,25,26,27].
In the search for an alternative and new procedure for the preparation of diastereomeric sulfinates derived from readily available sugars, we focused our attention on diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 [28] (Figure 1) and its reactivity with organometallic reagents.
The possibility of using this diastereoisomerically pure sulfite for the preparation of selected diastereoisomeric O-sulfinates results from our earlier observation that the reaction of prochiral sulfites with t-butylmagnesium chloride could be stopped on the stage of the corresponding sulfinic esters [29] and from the synthesis of enantiomerically enriched t-butanesulfinates 6 by the reaction of prochiral sulfites 5 with t-butylmagnesium chloride carried out in the presence of optically active aminoalcohols as a chiral complexing agent (Scheme 3) [30].

2. Results and Disscusion

Having in the hands diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4, synthesized from α-d-glucofuranose in the sequence of reactions, described earlier by one of us [28], we decided to check if its reactions with Grignard reagents could be stopped at the stage of the corresponding sulfinic acid esters. Reactions of 4 with methylmagnesium iodide 7a, phenylmagnesium bromide 7b, and p-tolylmagnesium bromide 7c did not afford optically active sulfinates 8a–c, but symmetrical sulfoxides 9a–c were obtained as products. This can be explained by assuming that precursors of sulfinates 8a–c, magnesium functionalized sulfinates 8′a–c generated in the first stage of the reaction, react immediately with another equivalent of Grignard reagents present in the reaction mixture (Scheme 4). In the case of benzylmagnesium bromide 7d, 1,2-diphenylethane was isolated as the main product. On the other hand, the reaction of (R)-4 with t-butylmagnesium chloride 7e stopped at the stage of sulfinate 10. When tetrahydrofuran, diethyl ether and benzene were used as solvents, the product was isolated as a single diastereoisomer, in 88%, 90%, and 85% yield, respectively (Scheme 5).
Analytically pure sulfinate (-)-10 was isolated by column chromatography (DCM: Et2O 1:1). Its 100% diastereoselective purity was confirmed by conversion (under conditions that preclude racemization of the substrate and product) into the known enantiomerically pure t-butyl methyl sulfoxide (+)-(R)-11 (Scheme 6) [25,31]. Given that the configuration at the stereogenic sulfur atom of sulfinate 10 is inverted during this reaction, its (S) absolute configuration could be suggested.
It is interesting to note that the reaction of sterically demanded Grignard reagents (such as 1-adamantylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, or 2,4,6-tri-tert-butylphenylmagnesium bromide) with diastereoisomerically pure sulfite (R)-4 did not occur, even if an excess of organometallics was used, and the reaction time at room temperature was prolonged up to 7 days. In these cases, the sulfite (R)-4 was recovered and the Grignard reagent used was converted into the corresponding hydrocarbon during reaction work-up. It should be noted that the recovery of diastereoisomerically pure sulfite (R)-4 indicates simultaneously a lack of racemization under the reaction conditions
To prove without a doubt the absolute configuration of sulfinate (-)-(S)-10 based on the chemical correlation discussed above its structure and absolute configuration at the stereogenic sulfur atom were determined by an X-ray structural analysis (see Figure 2). (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 crystallizes in an orthorhombic system, in space group P212121 (Table S1 in SI). The unit cell consists of four monomers. The absolute configuration at the chiral sulfur atom is S. The five-membered ring C1,C2,C3,C4,O4 adopts a half-chair conformation, while the ring C1,C2,O2,C7,O1 is an envelope, with the O2 atom being at the flap position. The angle of envelope opening is equal to 29.7°. The calculated values of the asymmetry parameters [32,33] for both rings are collected in Table S2 (see SI).
Comparison of the absolute configurations of the starting sulfite, (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4, and the structure of the corresponding (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 formed, clearly indicates that nucleophilic substitution at the stereogenic sulfur atom occurs with the full inversion of configuration. This can be explained by the reaction sequence which is shown below in the Scheme 7 and by assumption that the intermediate 4C has a trigonal bipyramidal structure. According to this mechanistic proposal, discussed in details in our recent paper [34], the observed inversion of configuration is caused by the presence of both the entering t-butyl substituent and the leaving O-α-d-glucofuranosyl group in the apical positions of this intermediate. This mechanistic proposal (in which we assume the monomeric nature of t-butylmagnesium chloride) also explains why the regioisomeric t-butanesulfinate 12, the formation of which, via the intermediate 4E, is shown in the upper part of Scheme 7 was not observed in all experiments carried out in THF, Et2O, nor benzene. This is because the formation of the 4E intermediate is unfavorable due to the steric repulsion between t-butyl group and O-α-d-glucofuranosyl group in an equatorial position.
An interesting feature, which is shown in Figure 2, is the presence of a strong O-H...O interaction between oxygen atoms O3 and O11. The distance O3---O11 is 2.888 Å (for other details, see Figure 3). This might be related to the inversion of configuration of the S atom. Besides the intramolecular O3-H(3)---O11 hydrogen bond, there is also an intermolecular O6-H(6)...O3SYM (1+x, y, z) hydrogen bond, building a linear chain parallel to the a axis. The distance O6---O3SYM is 2.800 Å (for other details, see Figure 3).
Figure 2 presents the large ellipsoids of the atoms of terminal groups (atom C7 and its attachments C71, C72), most likely due to the increased mobility of that region. This mobility increase seems to be an effect of the involvement of the remaining (stable) region of the molecule in two strong intra- and intermolecular hydrogen bonding systems which result in good stability. Therefore, the regions which are not involved in that H-bonding system are forced to be highly mobile.

3. Materials and Methods

All reactions were carried out under argon atmosphere using gun vacuum dried glassware. Dry solvents were degassed before the use. All commercial reagents were purchased from Aldrich (Darmstadt, Germany) and TCI (Tokyo Chemica Industry, Tokyo, Japan). Dry solvents were prepared according to standard procedures. Reactions were followed using thin layer chromatography (TLC) on silica gel-coated plates (Merck 60 F254) with the indicated solvent mixture. Optical rotations were measured on a Perkin-Elmer 241 MC polarimeter (Vienna, Austria) (c = 1). Column chromatography was carried out using Merck 60 (40–63 or 230–400 mesh) silica gel. 1H NMR spectra were recorded at 200 MHz in CDCl3 as solvent. 1H NMR chemical shifts are given in ppm with respect to tetramethylsilane (TMS) as an internal standard.

3.1. (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl-α-d-Glucofuranose (R)-4 [28]

6-O-tert-Butyldimethylsilyl-1,2-O-isopropylidene-α-d-glucofuranose (3.4 g, 10 mmol) in pyridine (10 mL) was treated with freshly distilled thionyl chloride (0.87 mL, 12 mmol). The mixture was kept at 0 °C, and after disappearance of the substrate (24 h) the mixture was poured into water and extracted with DMC. The extract was dried over MgSO4, concentrated in vacuo and separated on silica gel column using n-hexane-diethyl ether (9:1) as an eluent to give (R)-4 (1.5 g, 45%), m.p. = 54–56 °C, [α]D = +48.0 (c = 1.4 CH2Cl2), 1H NMR (CDCl3): δ = 6.01 (d, 1H, J = 3.8 Hz, H-1); 4.94 (d, 1H, J = 2.6 Hz, H-3); 4.68 (d, 1H, J = 3.8 Hz, H-2); 4.46 (t, 1H, J = 2.6, 5.5 Hz, H-4); 4.30 (m, 1H, J = 4.8, 5.5, 8.0 Hz, H-5); 4.12 (dd, 1H, J = 8.0, 10.8 Hz, H-6); 3.93 (dd, 1H, J = 4.8, 10,8 Hz, H-6); 1.50, 1.35 (2s, 6H, 2×CH3); 0.89 (s, 9H, t-Bu); 0.08 (s, 6H, 2×CH3).

3.2. (S)-1,2-O-Isopropylidene-(5-O-α-d-glucofuranosyl) t-Butanesulfinate (-)-(S)-10

(1 mmol, 0.226 g) of (R)-4 in 10 mL of a solvent (THF, Et2O or benzene) was cooled to 0 °C and treated with excess of t-butylmagnesium chloride (3 mmol). The progress of the reaction was monitored with TLC. After 4 h for Et2O and THF as the solvents (and 6 h for benzene as a solvent), the mixture was worked up with 10 mL of saturated ammonium chloride and extracted 3 times with DCM (3 × 10 mL). Combined extracts were dried over magnesium sulfate and evaporated. Separated on silica gel column using DCM: Et2O 1:1 as an eluent gave desired product 10: 0.291 g (90% for Et2O as a solvent), 0.285 g (88% for THF as a solvent), and 0.275 g (85% for benzene as a solvent). M.p. = 60–62 °C, [α]D = −57.8 (c = 1.0 DCM). 1H NMR (CDCl3): δ = 5.95 (d, 1H, J = 3.5 Hz, H-1); 4.56 (d, 1H, J = 3.5 Hz, H-3); 4.41 (d, 1H, J = 2.2 Hz, H-2); 4.38 (s, 1H, OH); 4.35 (d, 1H, J = 3.6 Hz, H-4); 4.21 (dd, 1H, J = 2.4, 9.7 Hz, H-5); 4.17 (d.d, 1H, J = 2.4, 7.3 Hz, H-6); 4.06 (dd, 1H, J = 3.4, 8.7 Hz, H-6); 3.99 (d, 1H, J = 3.5 Hz, H-5); 1.55, 1.62 (br, s, 1H, OH); 1.50 (s, 3H, OCH3); 1.31 (s, 3H, OCH3); 1.23 (s, 9H, t-Bu). Anal. Calcd. for C13H24O7S: C, 48.15; H, 7.41; S, 9.87. Found: C, 48.41; H, 7.23; S, 9.99.

3.3. t-Butyl Methyl Sulfoxide (+)-(R)-11

A solution of (-)-(S)-10 (0,162 g, 0.5 mmol) in 10 mL of diethyl ether was added dropwise to an etheral solution of methylmagnesium iodide (1 mmol/10 mL) at room temperature. After completion of the addition, the reaction mixture was stirred for 2 h at room temperature. The reaction was then quenched with 10 mL saturated ammonium chloride solution. After being stirred for a while, the layers were separated and the ether phase was extracted twice with water (2 × 10 mL). The combined water phases, after saturation with sodium chloride, were extracted with dichloromethane (4 × 10 mL). The organic solution was dried over magnesium sulfate and evaporated. A crude product was purified on a silica gel column using dichloromethane - ethyl ether (2:1) as eluent affording (-)-(R)-t-butyl methyl sulfoxide 11 (54 mg, 90%) [α]D = −4.2 (c = 1.0, acetone), 99% e.e.; 1H NMR (CDCl3): 2.28 (s, 3H); 1.15 (s, 9H). These data are fully consistent with the literature data [25,28].

3.4. Reaction of (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl- α-d-Glucofuranose (+)-(R)-4 with Phenylmagnesium Bromide

A solution of (+)-(R)-4 (0.133 g, 0.5 mmol) in of THF (5 mL) was cooled to 0 °C and treated with a solution of freshly prepared phenylmagnesium bromide (1.5 mmol) in THF (10 mL). The progress of the reaction was monitored with TLC and after disappearance of the substrate (1.5 h) the mixture was treated with aqueous, saturated ammonium chloride solution (7 mL) and extracted with chloroform (4 × 10 mL). The combined organic phase was dried over magnesium sulfate and evaporated. The residue was separated on a silica gel column using DCM: ethyl acetate 2:1 and, finally, with ethyl acetate as eluents for diphenyl sulfoxide 9b (88 mg, 89%) m.p. 69–71 °C; 1H NMR (CDCl3): δ = 7.22–7.36 (m, 6H), 7.47–7.62 (m, 4H) (these data are in accordance with literature data [35,36,37]) and 1,2-O-isopropylidene-α-d-glucofuranose 13 (71 mg, 65% [α]D = −11.2 (c = 1.2, H2O- this value is in accordance with literature data [38]). Substrate (+)-(R)-4 was not detected. A similar reaction of (+)-(R)-4 (0.133 g, 0.5 mmol) with p-toluenemagnesium bromide (1.5 mmol) afforded di-p-tolyl sulfoxide 9c (92 mg, 80%) m.p. 92–94 °C; 1H NMR (CDCl3): δ = 2.35, 7.25, and 7.52 (AB system, J = 7.2 Hz, 4H) (these data are in accordance with literature data [39]).

3.5. Reaction of (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl-α-d-Glucofuranose (+)-(R)-4 with 2,4,6-tri-tert-Butylphenylmagnesium Bromide

A solution of (+)-(R)-4 (0.133 g, 0.5 mmol) in THF (5 mL) was treated with a solution of 2,4,6-tri-tert-butylphenylmagnesium bromide in THF (1.5 mmol) [40] at room temperature. The progress of the reaction was monitored with TLC. Stirring was continued for 7 days without observing the progress of the reaction, sulfite 4 was still observed. After this time, standard work-up with aqueous, saturated ammonium chloride solution (7 mL) and extraction with DCM (4 × 7 mL) gave an organic solution, which was dried over magnesium sulfate and evaporated. The residue was separated on a silica gel column using ethyl acetate -DCM (2:1) and finally ethyl acetate for the substrate (+)-(R)-4 (104 mg, 78%) and 1,3,5-tri-tert-butylbenzene 14 (158 mg, 86%) (1H NMR in accordance with literature data [41]). 1,2-O-isopropylidene-α-d-glucofuranose 13 (8 mg, 7%) was also isolated.

3.6. X-ray Crystallography of (S)-1,2-O-Isopropylidene-(5-O-α-d-glucofuranosyl)t-Butanesulfinate (-)-(S)-10

Crystal and molecular structure of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (-)-(S)-10 was determined using data collected at 100K with an Oxford Instruments KM4 diffractometer using MoKα radiation (Oxford, UK) [42]. The lattice constants were refined by least-squares fit of 17405 reflections collected in the Ø range 3.67–36.14° [43]. A total of 6250 independent reflections were used to solve the structure by direct methods and to refine it by full matrix least-squares using F2 [44]. Hydrogen atoms attached to non-carbon atoms were found in a difference Fourier map and refined isotropically. Hydrogen atoms attached to carbon atoms were placed geometrically at idealized positions and refined isotropically, except for the H atoms at the C72 carbon in which Uiso parameters were constrained with their parent atom. Anisotropic thermal parameters were refined for all nonhydrogen atoms. The Coot and Mercury (Cambridge, UK) programs were used for model building and structure visualization [45,46]. The final refinement yielded the values of R1 = 0.0633 and wR2 = 0.1440 for 263 refined parameters and 5270 observed reflections. The absolute structure was determined by the Flack method [47,48], and the Flack parameter was x = –0.11(9). The calculated parameters for inverted structure, i.e., with assumed opposite (incorrect) chirality, were: R1(inv) = 0.0643, wR2(inv) = 0.1561, and x(inv) = 1.06(9). Compound crystallizes in the orthorhombic system, space group P212121, with the unit cell consisting of four monomers. Crystal data and experimental details are shown in Table S1 (see SI). The absolute configurations at the stereogenic atoms are SS1, RC1, RC2, SC3, SC4, RC5.

Supplementary Materials

Table S1: Crystal data and experimental details for (S)-1,2-O-isopropylidene-(5-O-α-D-glucofuranosyl) t-butanesulfinate 10; Table S2: Asymmetry parameters for the two five-membered rings in the crystal structure of (S)-1,2-O-isopropylidene-(5-O-α-D-glucofuranose) t-butanesulfinate 10. CCDC-229829 contains the supplementary crystallographic data for this paper (for (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10). These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by mail to [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(0)1223-336033.

Author Contributions

Conceptualization, J.D.; Methodology, B.B., J.D., J.B.; Investigation, J.D., J.B., B.B., M.C.; Resources, J.D., M.C.; Writing—Original Draft Preparation, J.D., J.B., B.B.; Writing—J.D., J.B., B.B.; Supervision, J.D.; Funding Acquisition, J.D., M.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded in part by the National Science Center, grant number UMO-2014/15/B/ ST5/05329 (for J.D.), and the APC was funded by Molecules Journal.

Acknowledgments

We thank Agnieszka D. Filipczak, and Wiesław R. Majzner, from Institute of Technical Biochemistry, Łódź University of Technology, Poland, for data collection and preliminary structure determination. J.B. also thanks Michał W. Wieczorek, from Łódź University of Technology, Poland, for his great support and continuous encouragement. We also want to thank Dorota Krasowska for the final correction of the manuscript’s graphic.

Conflicts of Interest

The authors declare no competing financial interest. The sponsors had no role in the design, execution, interpretation, or writing of the study.

References

  1. Drabowicz, J.; Kiełbasiński, P.; Mikołajczyk, M. Sulphinic acids and esters in synthesis. In The Chemistry of Sulfinic Acid, Esters and Their Derivatives; Patai, S., Ed.; John Wiley & Sons: Chichester, UK, 1990; pp. 351–429. [Google Scholar] [CrossRef]
  2. Mikołajczyk, M.; Drabowicz, J.; Kiełbasiński, P. Chiral Sulfur Reagents; CRC Press: Boca Raton, FL, USA, 1997; ISBN 9780849391200. [Google Scholar]
  3. Mikołajczyk, M.; Drabowicz, J. Chiral organosulfur compounds. Top. Stereochem. 1982, 13, 333–468. [Google Scholar] [CrossRef]
  4. Nudelman, A. Sulfinic acids and their derivatives. Stereochemistry and chiroptical properties. In The Chemistry of Sulfinic Acids, Esters and Their Derivatives; Patai, S., Ed.; John Wiley & Sons: Chichester, UK, 1990; pp. 35–85. [Google Scholar] [CrossRef]
  5. Zoller, U. Syntheses of sulfinic esters. In The Chemistry of Sulfinic Acids, Esters and Their Derivatives; Patai, S., Ed.; John Wiley & Sons: Chichester, UK, 1990; pp. 217–237. [Google Scholar] [CrossRef]
  6. Nudelman, A. Chemistry of Optically Active Sulfur Compounds; Gordon and Breach Science Publishers Inc.: New York, NY, USA, 1984. [Google Scholar]
  7. Wenschuh, E.; Dölling, K.; Mikołajczyk, M.; Drabowicz, J. Aktuelle ergebnisse zur synthese und reaktivitat der sulfinsuaren und ihrer derivate. Z. Chem. 1980, 20, 122–132. [Google Scholar] [CrossRef]
  8. Drabowicz, J.; Krasowska, D.; Zając, A. Advances in the synthesis of chiral sulphinyl derivatives. Spec. Chem. Mag. 2007, 27, 34–37. [Google Scholar]
  9. Wei, J.; Sun, Z. Tert-butyl sulfoxides as a starting point for the synthesis of sulfinyl containing compounds. Org. Lett. 2015, 17, 5396–5399. [Google Scholar] [CrossRef] [PubMed]
  10. He, Y.; Zhang, J.; Liang, X.; Wei, Y. Electrochemical synthesis of sulfinic esters from alcohols and thiophenols. Tetrahedron Lett. 2020, 61. [Google Scholar] [CrossRef]
  11. Zhou, C.; Tan, Z.; Jiang, H.; Zhang, M. A sustainable oxidative esterification of thiols with alcohols by a cobalt nanocatalyst supported on doped carbon. Green Chem. 2018, 20, 1992–1997. [Google Scholar] [CrossRef]
  12. Gafur, S.H.; Waggoner, S.L.; Jacobsen, E.; Hamaker, C.G.; Hithcock, S.R. Efficient synthesis of sulfinate esters and sulfinamides via activated esters of p-toluenesulfinic acid. Synthesis 2018, 50, 4855–4866. [Google Scholar] [CrossRef] [Green Version]
  13. Tranquilino, A.; Andrade, S.R.C.P.; da Silva, A.P.M.; Menezes, P.H.; Oliveira, R.A. Non-expensive, open-flask and selective catalytic systems for the synthesis of sulfinate esters and thiosulfonates. Tetrahedron Lett 2017, 58, 1265–1268. [Google Scholar] [CrossRef]
  14. Fragher, R.J.; Shkoor, M.; Luska, L.; Schwan, A.L. Unexpected Reactions of Grignard Reagents with Selected β-Carboalkoxy Substituted Sulfinate Esters. Can. J. Chem. 2015, 93, 37–43. [Google Scholar] [CrossRef]
  15. Wojaczynska, E.; Wojaczynski, J. Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds. Chem. Rev. 2020, 120, 4578–4611. [Google Scholar] [CrossRef] [PubMed]
  16. Phillips, H. CCCLIV.-Investigations on the dependence of rotatory power on chemical constitution. Part XXVII. The optical properties of n-alkyl p-toluenesulphinates. J. Chem. Soc. Trans. 1925, 127, 2552–2587. [Google Scholar] [CrossRef]
  17. Drabowicz, J.; Krawczyk-Sójka, E.; Jasiak, A.; Krasowska, D.; Mielniczak, G.; Koprowski, M.; Owsianik, K. Process for the Preparation of Diastereomerically Pure O-(1R, 2S, 5R)-mentyl p-toluenesulfinate with Absolute Configuration (S). Polish Patent No. P.433225, 12 March 2020. [Google Scholar]
  18. Jasiak, A. Metody Przepływowe w Syntezie Chiralnych i Achiralnych związków Heteroorganicznych. Ph.D. Thesis, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Lodz, Poland, 2020. [Google Scholar]
  19. Andersen, K.K. Synthesis of (+)-ethyl p-tolyl sulfoxide from (-)-menthyl (-)-p-toluenesulfinate. Tetrahedron Lett. 1962, 3, 93–95. [Google Scholar] [CrossRef]
  20. Andersen, K.K.; Gaffield, W.; Papanikolaou, N.E.; Foley, J.; Perkins, R.I. Optically active sulfoxides. The synthesis and rotatory dispersion of some diaryl sulfoxides. J. Am. Chem. Soc. 1964, 86, 5637–5646. [Google Scholar] [CrossRef]
  21. Andersen, K.K. Configurational relationships among some sulfoxides. J. Org. Chem. 1964, 29, 1953–1956. [Google Scholar] [CrossRef]
  22. Ridley, D.D.; Smal, M.A. Use of carbohydrates in the preparation of optically active sulphoxides. J. Chem. Soc. Chem. Commun. 1981, 505–506. [Google Scholar] [CrossRef]
  23. Ridley, D.D.; Smal, M.A. Preparation of arenesulfinic esters of 1,2:5,6-Di-O-cyclohexylidene-α-D-glucofuranose, and their conversion into optically active sulfoxides. Aust. J. Chem. 1982, 35, 495–507. [Google Scholar] [CrossRef]
  24. Llera, J.M.; Fernandez, I.; Alcudia, F. An efficient synthesis of both enantiomers of chiral non racemic methylsulfoxides from DAG. Tetrahedron Lett. 1991, 32, 7299–7302. [Google Scholar] [CrossRef]
  25. Fernandez, I.; Khiar, N.; Llera, J.M.; Alcudia, F. Asymmetric synthesis of alkane- and arenesulfinates of diacetone-D-glucose (DAG): An improved and general route to both enantiomerically pure sulfoxides. J. Org. Chem. 1992, 57, 6789–6796. [Google Scholar] [CrossRef]
  26. Khiar, N.; Fernandez, I.; Alcudia, F. Asymmetric synthesis of optically pure tert-butyl sulfoxides using the “DAG methodology”. Tetrahedron Lett. 1994, 35, 5719–5722. [Google Scholar] [CrossRef]
  27. Khiar, N. Determination of the absolute configuration of sulfinyl glycosides: The role of the exo-anomeric effect. Tetrahedron Lett. 2000, 41, 9059–9063. [Google Scholar] [CrossRef]
  28. Borsuk, K.; Frelek, J.; Łysek, R.; Urbańczyk-Lipkowska, Z.; Chmielewski, M. Six-membered cyclic sulfites derived from glucofuranose and 1,2,4-butanetriol. Chirality 2001, 13, 533–540. [Google Scholar] [CrossRef] [PubMed]
  29. Drabowicz, J.; Mikołajczyk, M. One-step synthesis of alkyl t-alkanesulfinates. Synthesis 1974. [Google Scholar] [CrossRef]
  30. Drabowicz, J.; Legędź, S.; Mikołajczyk, M. Organosulphur compounds LXIX: Optically active sulphinates: A new type of enantioselective asymmetric synthesis and kinetic resolution. Tetrahedron 1988, 44, 5243–5251. [Google Scholar] [CrossRef]
  31. Pitchen, P.; Dunsch, E.; Desmukh, M.N.; Kagan, H.B. An efficient asymmetric oxidation of sulfides to sulfoxides. J. Am. Chem. Soc. 1984, 106, 8188–8193. [Google Scholar] [CrossRef]
  32. Cremer, D.; Pople, J.A. General definition of ring puckering coordinates. J. Am. Chem. Soc. 1975, 97, 1354–1358. [Google Scholar] [CrossRef]
  33. Nardelli, M. Ring asymmetry parameters from out-of-plane atomic displacements. Acta Cryst. 1983, 39, 1141–1142. [Google Scholar] [CrossRef]
  34. Bujnicki, B.; Drabowicz, J.; Mikolajczyk, M. Acid catalyzed alcoholysis of sulfinamides: Unusual stereochemistry, kinetics and a question of mechanism involving sulfurane intermediates and their pseudorotation. Molecules 2015, 20, 2949–2972. [Google Scholar] [CrossRef] [Green Version]
  35. Drabowicz, J.; Łyżwa, P.; Popielarczyk, M.; Mikołajczyk, M. A convenient procedure for oxidation of sterically hindered sulfides to sulfoxides. Synthesis 1990, 937–938. [Google Scholar] [CrossRef]
  36. Safaiee, M.; Moeinimehr, M.; Zolfigol, M.A. Pyridiniumporphyrazinato oxo-vanadium tribromomethanide as a newsource of Br+ catalyst for the chemo and homoselective oxidation of sulfides and benzylic alcohols. Polyhedron 2019, 170, 138–150. [Google Scholar] [CrossRef]
  37. He, Y.; Ma, X.; Ji, H.F.; Zha, X.B.; Jiang, H.; Lu, M. Selective Oxidation of Sulfides to Sulfoxides/Sulfones by 30% Hydrogen Peroxide. Phosphorus Sulfur Silicon Relat. Elem. 2012, 187, 822–830. [Google Scholar] [CrossRef]
  38. Reddy, A.B.; Swamy, B.K.; Yadav, J.S. A concise synthesis of cleistenolide. Tetrahedron Asymmetry 2016, 27, 788–790. [Google Scholar] [CrossRef]
  39. Laali, K.K.; Nagvekar, D.S. Reaction of simple arenes with FSO3H·SbF5/SO2: One-pot synthesis of aromatic sulfoxides. Mechanistic aspects and synthetic utility. J. Org. Chem. 1991, 56, 1867–1874. [Google Scholar] [CrossRef]
  40. Davis, F.A.; Jenkins Jr., R.H.; Rizvi, S.Q.A.; Yocklovich, S.G. Chemistry of sulfenic acids. 3. Studies of sterically hindered sulfenic acids using flash vacuum pyrolysis. J. Org. Chem. 1981, 46, 3467–3474. [Google Scholar] [CrossRef]
  41. Bresien, J.; Hinz, A.; Schulz, A.; Suhrbier, T.; Thomas, M.; Villinger, A. Dichloro-cycloazatriphosphane: The missing link between N2P2 and P4 ring systems in the systematic development of NP chemistry. Chem. Eur. J. 2017, 23, 14738–14742. [Google Scholar] [CrossRef]
  42. KM4CCD CrysAlis CCD, Data Collection Program. Version 1.163. Unilic & Kuma Diffraction Instruments: GmbH, Wroclaw, Poland, 2000.
  43. KM4CCD CrysAlis RED, Data Reduction Program. Version 1.163. Unilic & Kuma Diffraction Instruments: GmbH, Wroclaw, Poland, 2000.
  44. Sheldrick, G.M. Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 3–8. [Google Scholar] [CrossRef]
  45. Emsley, P.; Lohkamp, B.; Scott, W.G.; Cowtan, C. Features and development of Coot. Acta Cryst. 2010, 66, 486–501. [Google Scholar] [CrossRef] [Green Version]
  46. Macrae, C.F.; Bruno, I.J.; Chisholm, J.A.; Edgington, P.R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P.A. Mercury CSD 2.0 - new features for the visualization and investigation of crystal structures. J. Appl. Cryst. 2008, 41, 466–470. [Google Scholar] [CrossRef]
  47. Flack, H.D. On enantiomorph-polarity estimation. Acta Cryst. 1983, 39, 876–881. [Google Scholar] [CrossRef]
  48. Parsons, S.; Flack, H.D.; Wagner, T. Use of intensity quotients and differences in absolute structure refinement. Acta Cryst. 2013, B69, 249–259. [Google Scholar] [CrossRef] [PubMed] [Green Version]
Sample Availability: Samples of the compound 10 are available from the authors.
Molecules 25 03392 sch001 550
Scheme 1. Synthesis of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a.
Scheme 1. Synthesis of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a.
Molecules 25 03392 sch001
Molecules 25 03392 sch002 550
Scheme 2. Sulfinylation of dicyclohexylidene α-d-glucose (DCG) and diacetone α-d-glucose (DAG).
Scheme 2. Sulfinylation of dicyclohexylidene α-d-glucose (DCG) and diacetone α-d-glucose (DAG).
Molecules 25 03392 sch002
Molecules 25 03392 g001 550
Figure 1. (R)-1,2-O -isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4.
Figure 1. (R)-1,2-O -isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4.
Molecules 25 03392 g001
Molecules 25 03392 sch003 550
Scheme 3. Synthesis of enantiomerically enriched t-butanesulfinates 6.
Scheme 3. Synthesis of enantiomerically enriched t-butanesulfinates 6.
Molecules 25 03392 sch003
Molecules 25 03392 sch004 550
Scheme 4. Reactions of sulfite (R)-4 with Grignard reagents 7a–d.
Scheme 4. Reactions of sulfite (R)-4 with Grignard reagents 7a–d.
Molecules 25 03392 sch004
Molecules 25 03392 sch005 550
Scheme 5. Fully diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium chloride 7e.
Scheme 5. Fully diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium chloride 7e.
Molecules 25 03392 sch005
Molecules 25 03392 sch006 550
Scheme 6. Fully stereoselective reaction of sulfinate (S)-10 with methymagnesium iodide 7a.
Scheme 6. Fully stereoselective reaction of sulfinate (S)-10 with methymagnesium iodide 7a.
Molecules 25 03392 sch006
Molecules 25 03392 g002 550
Figure 2. Molecular structure of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate 10. The thermal ellipsoids are shown with 50% probability. Temperature of data collection was 100 K. The free electron pair at the sulfur atom is behind the Figure plane.
Figure 2. Molecular structure of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate 10. The thermal ellipsoids are shown with 50% probability. Temperature of data collection was 100 K. The free electron pair at the sulfur atom is behind the Figure plane.
Molecules 25 03392 g002
Molecules 25 03392 sch007 550
Scheme 7. Proposed mechanism for diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium chloride.
Scheme 7. Proposed mechanism for diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium chloride.
Molecules 25 03392 sch007
Molecules 25 03392 g003 550
Figure 3. The two strong O-H...O interactions between oxygen atoms: O3 and O11 (intramolecular) and between O6 and O3SYM (intermolecular, SYM = 1 + x,y,z), in the crystal lattice of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate 10. The interaction between O6 and O3SYM creates a linear chain extending through entire lattice along a axis. The distance O3---O11 is 2.888 Å, and the distance O6---O3SYM is 2.800 Å.
Figure 3. The two strong O-H...O interactions between oxygen atoms: O3 and O11 (intramolecular) and between O6 and O3SYM (intermolecular, SYM = 1 + x,y,z), in the crystal lattice of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate 10. The interaction between O6 and O3SYM creates a linear chain extending through entire lattice along a axis. The distance O3---O11 is 2.888 Å, and the distance O6---O3SYM is 2.800 Å.
Molecules 25 03392 g003

Share and Cite

MDPI and ACS Style

Bujnicki, B.; Błaszczyk, J.; Chmielewski, M.; Drabowicz, J. Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity. Molecules 2020, 25, 3392. https://doi.org/10.3390/molecules25153392

AMA Style

Bujnicki B, Błaszczyk J, Chmielewski M, Drabowicz J. Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity. Molecules. 2020; 25(15):3392. https://doi.org/10.3390/molecules25153392

Chicago/Turabian Style

Bujnicki, Bogdan, Jarosław Błaszczyk, Marek Chmielewski, and Józef Drabowicz. 2020. "Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity" Molecules 25, no. 15: 3392. https://doi.org/10.3390/molecules25153392

Article Metrics

Back to TopTop