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Complimentary and Personal Copy Complimentary and personal copy www.thieme.com SYNTHESIS Reviews and Full Papers in Chemical Synthesis This electronic reprint is provided for non- commercial and personal use only: this reprint may be forwarded to individual colleagues or may be used on the author’s homepage. This reprint is not provided for distribution in repositories, including social and scientific networks and platforms. Publishing House and Copyright: © 2018 by Georg Thieme Verlag KG Rüdigerstraße 14 70469 Stuttgart ISSN 0039-7881 Any further use only by permission of the Publishing House SYNTHESIS0039-78811437-210X © Georg Thieme Verlag Stuttgart · New York 2018, 50, 3337–3343 psp 3337 en Syn thesis M. P. Ó Fearraigh et al. PSP Synthesis of Isothiocineole and Application in Multigram-Scale Sulfur Ylide Mediated Asymmetric Epoxidation and Aziridination Martin P. Ó Fearraigha b Johnathan V. Matlock ++S8 b,c Ona Illa a,b Eoghan M. McGarrigle* 0000-0001-8160-6431 Ts N O Varinder K. Aggarwal*b H S a Centre for Synthesis and Chemical Biology, UCD School of Chemistry, University College Dublin, Belfield, Dublin 4, isothiocineole 25 g scale Ireland [email protected] b School of Chemistry, University of Bristol, Cantock’s Close, Ts Bristol, BS8 1TS, UK >5 g scale N O >5 g scale high d.r. high d.r. S [email protected] high e.r. Ph Ph Ph Ph high e.r. c Departament de Química, Universitat Autònoma de Barce- Ph –OTf lona, 08193 Cerdanyola del Vallès, Spain 50 g scale Received: 18.06.2018 O O R2 2 Accepted: 21.06.2018 + R2S R Published online: 19.07.2018 R1 R1 DOI: 10.1055/s-0037-1609580; Art ID: ss-2018-z0422-psp PG PG Abstract The synthesis of the chiral sulfide isothiocineole from limo- N N R2 2 nene and elemental sulfur on multi-gram scale and its alkylation to + R2S R 1 1 make >50 g of the corresponding benzylsulfonium salt are described. R R The application of this salt to the sulfur ylide-mediated asymmetric ep- Scheme 1 The sulfur ylide disconnection for epoxides and aziridines oxidation of aldehydes and the asymmetric aziridination of imines on a >5 g scale is demonstrated. Key words sulfur ylide, asymmetric epoxidation, asymmetric aziridi- nation, chiral sulfide gree of racemization occurred leading to sulfide that was less enantiopure than the limonene precursor. Under these original conditions the limonene acts as a source of hydro- The use of sulfur ylides to synthesize epoxides and aziri- gen as well as a source of the carbon skeleton of 1. Sulfide 2 dines represents a valuable strategic disconnection wherein was also formed as an undesired by-product and was quite both a C–C bond and a C–heteroatom bond are made in a difficult to separate from 1. We found that readily available single step (Scheme 1).1 It provides an alternative route to γ-terpinene (3) acts as a source of hydrogen atoms enabling these valuable synthetic intermediates, which is comple- milder conditions to be used, which gave no loss in enantio- mentary to alkene oxidation processes.2 We have shown specificity, and no sulfide 2 was generated. However, the γ- that isothiocineole (1) is an effective chiral sulfide for use in terpinene is also consumed by side-reactions and thus sev- asymmetric epoxidations and aziridinations.2,3 We have eral equivalents are required. Reaction monitoring led us to demonstrated a wide reaction scope, and delineated the discover that adding aliquots of γ-terpinene and sulfur factors that affect enantioselectivity and diastereoselectivi- during the reaction led to higher yields of isothiocineole (1). ty. This enables isothiocineole (1) to be employed with con- The γ-terpinene is converted into p-cymene by the reaction fidence in a synthetic plan. Furthermore it can be made in and can be separated from the product by distillation. We one step from sulfur and limonene, and is now commercial- had found that 1,4-cyclohexadiene also can fulfil this role ly available. Indeed since our first publication, several other but it is more expensive and we wanted to avoid the pro- groups have made use of this sulfide in epoxidations, aziri- duction of stoichiometric quantities of benzene. Limonene dinations, and other reactions that required a chiral sul- is readily available in both enantiomeric forms at low cost. fide.4 The S-enantiomer is normally available as a 90:10 mixture Isothiocineole (1) had previously been made in the of enantiomers. (+)-Isothiocineole with e.r. 99:1 can be ob- 1930s and 1950s using simply limonene and sulfur tained through low-temperature recrystallization of 90:10 (Scheme 2).5,6 However, under the reported conditions a de- mixtures from pentane.3 © Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, 3337–3343 3338 Syn thesis M. P. Ó Fearraigh et al. PSP 2,3,7 a) Original synthesis of isothiocineole (1) are suitable substrates. We note that chromatography on large scale reactions with the sulfide can prove trouble- 170 °C some (solvent mixtures, which seemed appropriate by TLC, +S8 + did not lead to good separation on flash columns in some 2 h S H S cases), so it is generally more convenient to remove remain- 1 2 20% ing aldehyde or sulfide by Kugelrohr distillation where pos- e.r. 99:1 e.r. 94:6 sible prior to column chromatography. b) Improved synthesis of isothiocineole (1) O KOH O + 125 °C S+ PhH MeCN–H2O (9:1) Ph Ph +S8 + –OTf 0 °C to 25 °C overnight Ph H S 45 1 75%, >95:5 trans/cis 3 28 g e.r. >99:1, 6 g (3 × 1 equiv 57% e.r. 99:1 at 0, 3, 6 h) e.r. 99:1 Ts Ts N K2CO3 Scheme 2 Syntheses of isothiocineole (1) N S + + MeCN H Ph 0 °C to 25 °C Ph Ph Ph –OTf 7 6 The procedure we describe allows the sulfide to be iso- 4 90%, trans/cis 95:5 lated in pure form by vigreux distillation. The complete sep- e.r. 98:2, 6 g aration from p-cymene can be difficult, however, in most Scheme 4 Asymmetric epoxidation of aldehydes and asymmetric aziri- instances the presence of small amounts of p-cymene does dination of imines using sulfonium salt 4 not interfere with subsequent reactions. If the sulfide is to be converted into a sulfonium salt as is described here then In summary, herein we have described the scaleable it is easier to separate the p-cymene after salt formation. synthesis of isothiocineole (1), and its application to the The subsequent salt formation reaction is quite robust asymmetric epoxidation aldehydes and aziridination of and high yielding (Scheme 3). We noted that the tetrafluo- imines using simple procedures. We have previously pro- roborate analogue of 4 showed poor solubility and hence vided a clear rationale of why the sulfide succeeds in pro- the triflate was favored. However, for other salts the tetra- viding high enantioselectivity and diastereoselectivity, and fluoroborate analogue can be made directly from the corre- described the wide scope for these reactions.2,3 We hope sponding alcohol using HBF4 in Et2O and those salts work the availability of this information will increase the use of well in the epoxidation and aziridination reactions – this the sulfur ylide disconnection in asymmetric synthesis. can be more cost effective in some cases. A non-nucleophil- ic counterion is favored to improve the stability of the salt. Reactions were monitored using analytical TLC, carried out using alu- minum-backed silica plates (60 F254) and the eluents stated; visualiza- LiOTf tion was accomplished using UV light (254 nm) and a stain of KMnO4 + BnBr S+ CH Cl /H O (3 g) in aq 1% NaOH (300 mL). Flash column chromatography was per- S 2 2 2 – formed using silica gel [Davisil, 230–400 mesh (40–63 μm)]. Products 1 Ph OTf 4 were concentrated in vacuo using both a Büchi rotary evaporator 88% (bath temperatures up to 50 °C) and a high vacuum line at r.t. Mass 53 g spectra were recorded by the University College Dublin, School of Scheme 3 Alkylation of sulfide 1 to form sulfonium salt 4 Chemistry mass spectrometry service. High-performance liquid chro- matography was performed on an Agilent Technologies 1260 series We describe our standard procedures for the synthesis instrument equipped with a 6 column-switching device, auto sam- pler, and multiple wavelength detector. 1H and 13C NMR spectra were of epoxides from aryl aldehydes, and for the synthesis of to- recorded in CDCl3 in 300 MHz or 400 MHz spectrometer. For quanti- syl aziridines (Scheme 4). In all cases excellent enantiose- 1 tative NMR spectroscopy, the H NMR sample was made up in CDCl3 lectivity is achieved. Although we have found that the sul- and submitted with a 25 s delay at pulse angle of 45°. fide is not suitable for use under catalytic conditions, we Benzaldehyde (≥99%, 25 mL) obtained from Sigma-Aldrich was note that the sulfide is inexpensive, and can be recovered in washed with aq 10% Na2CO3 (2 × 25 mL) until no more evolution of moderate-to-good yields in most cases so there is less im- CO2 was observed. It was then washed with sat. aq Na2SO3 followed by petus to develop a catalytic method. Finally, we note that H2O (25 mL), then dried (MgSO4) for 15 min before distilling under N2 the diastereoselectivity obtained in the aziridination shown atmosphere at reduced pressure.8 KOH (>85%) was obtained from in Scheme 4 (95:5) is our best example, but diastereomeric Fischer Scientific. The KOH was first weighed as pellets then ground using a pestle and mortar before immediately weighing the required ratios generally ranged from 3:1 to 9:1 in aziridinations.
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