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(9R,10S)-Dihydrosterculic Acid: Overcoming Spontaneous Protonation During Lithium-Sulfoxide Exchange

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(9R,10S)-Dihydrosterculic Acid: Overcoming Spontaneous Protonation During Lithium-Sulfoxide Exchange SYNOPEN2509-9396 Georg Thieme Verlag Stuttgart · New York 2018, 2, 168–175 paper 168 en Syn Open S. W. Shields et al. Paper Asymmetric and Regiospecific Synthesis of Isotopically Labelled Cyclopropane Fatty Acid (9R,10S)-Dihydrosterculic Acid: Overcoming Spontaneous Protonation During Lithium-Sulfoxide Exchange O O O Samuel W. J. Shieldsa Z S S S D3C 5 a,b Ar Ar D C Ar Peter H. Buist 3 5 HO2C a,b Y Jeffrey M. Manthorpe* 0000-0026-966-797 Y Y 5 5 5 deuterated Key Steps: dihydrosterculic acids a Carleton University, Department of Chemistry, 203 Steacie (a) Corey–Chaykovsky cyclopropanation 3 Y = H, Z = D Building,, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, (b) lithium–sulfoxide exchange + alkylation 4 Y = D, Z = H (c) lithium–sulfoxide exchange + protonation/deuteration Canada b Carleton University, Institute of Biochemistry, 209 Nesbitt Rapid protonation side reaction in lithium–sulfoxide exchange + deuteration: Building, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, O t-BuLi, –78 °C, time then Canada S Z XS MeOD, –78 °C – r.t., 1 h [email protected] D3C 5 D3C 5 time Z (% D) H H 5 10 min <5 5 10 s 84 Received: 12.01.2018 therapeutic target.10 The proposed mechanism for cis-cy- Accepted after revision: 14.03.2018 clopropane to cyclopropene bioconversion involves step- Published online: 08.06.2018 DOI: 10.1055/s-0036-1591976; Art ID: so-2018-d0004-op wise hydrogen removal in a manner similar to that estab- License terms: lished for the desaturase-mediated dehydrogenation of cis- 11 olefinic fatty acids to give acetylenic products; however, Abstract The total synthesis of isotopically labelled (9R,10S)-dihydro- further details, including the cryptoregiochemistry of this sterculic acid, a usual cyclopropane fatty acid with biologically relevant process (i.e., which hydrogen is removed first), have not toxicity upon desaturation in vivo, is reported. A diastereoselective been elucidated. The situation is complicated by the fact Corey–Chaykovsky reaction was employed to form the cyclopropane that the putative cyclopropane fatty acid desaturases have ring. Rapid quenching of a lithium-sulfoxide exchange was required to achieve the requisite high levels of deuterium incorporation. not been isolated or characterised. Nevertheless, as part of our ongoing interest in fatty acid desaturation12 and cyclo- Key words lithium-sulfoxide exchange, deuterium labelling, asym- propane fatty acids13–15 we have undertaken a mechanistic metric Corey–Chaykovsky cyclopropanation, cyclopropane fatty acids, study of the biochemical desaturation of 1 to 2 (Figure 1). mechanistic probes, fatty acid desaturation Herein, we report the asymmetric synthesis of deuterium- labelled dihydrosterculic acids appropriate for use in evalu- Cyclopropane fatty acids, such as (9R,10S)-dihydroster- ating the individual primary kinetic isotope effects on C–H culic acid (1) are a structurally unique class of fatty acids bond cleavage at C9 and C10. produced by a variety of organisms.1 The presence of their cyclopropane ring confers oxidative stability to lipidic en- H H O sembles relative to their olefinic counterparts while main- 1 OH taining favourable biophysical properties, such as mem- O brane fluidity, and greater tolerance of low pH.2 Interesting- OH ly, in some plant species, cis-cyclopropane fatty acids are 2 thought to be converted into the corresponding cyclopro- Figure 1 Structures (9R,10S)-dihydrosterculic acid (1) and sterculic pene compounds via a unique syn-dehydrogenation (desat- acid (2) uration) reaction. Such cyclopropene fatty acids are potent inhibitors of mammalian stearoyl CoA Δ9 desaturases (SCDs). Humans have two SCD homologues – SCD1 and Our synthetic plan for the asymmetric synthesis of deu- SCD5. The X-ray structure of both human3 and murine4 terium-labelled dihydrosterculic acids 3 and 4 involved variants of SCD1 were recently published. Mice deficient in preparation of cyclopropyl bis(sulfoxides) 5 and 6 via a di- SCD1 demonstrated improved insulin sensitivity and lipid astereoselective cyclopropanation of α,β-unsaturated chiral 5,6 metabolic profiles when fed a high-fat diet and dysregula- bis(sulfoxide) (7/8) derived from readily accessible (SS,SS)- tion of SCD1 in humans has implications in diabetes,7 meta- 1,1-bis(p-toluenesulfinyl)methane 9, followed by regio- bolic syndrome,8 and cancer;9 therefore, SCD1 is an active Georg Thieme Verlag Stuttgart · New York — SynOpen 2018, 2, 168–175 169 Syn Open S. W. Shields et al. Paper selective lithium-sulfoxide exchange and alkylation.16 moved from the crude reaction mixture by rapid filtration Quenching with a proton or deuteron source would follow a through a silica plug, as the unlabelled isotopologue of 13 second lithium-sulfoxide exchange (Scheme 1).14,17 was known to undergo Mislow–Evans rearrangement upon prolonged exposure to silica gel.14,18,19 The resultant mix- 18 Z ture of 12 and 13 was exposed to a water-soluble carbo- D3C 10 3 Y, Z = H, D 19 9 4 Y, Z = D, H diimide to complete the conversion into 13, which was HO2C 1 Y again passed through a silica plug and immediately exposed to Corey–Chaykovsky cyclopropanation conditions. This Z D3C produced two cyclopropane diastereomers in an 85:15 ra- tio, with the major product being the desired diastereomer Y 6, which was isolated in 43% yield over three steps, with the final step requiring iterative chromatography to remove the O O minor diastereomer completely. S S 5 Y = H 6 Y = D O O Y S S 9 a O O S S O O O O 7 Y = H S S S S Y 8 Y = D + OH D D 12 13 5 5 b,c O O O S S + O O Y 9 S S Scheme 1 Retrosynthesis of isotopically labelled dihydrosterculic acids D 3 and 4 6 5 Synthesis of our 9-deuterio isotopologue 4 required Scheme 3 Reagents and conditions: (a) n-BuLi, THF, –50 °C to –40 °C, 1 dec-9-enal-1-d (11), which was prepared from dec-9-en-1- h; –78 °C, 15 min; 11, –78 °C, 30 min; (b) CuCl2 (cat.), N-cyclohexyl-N′- ol (Scheme 2). Jones oxidation and Fischer esterification (2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate, MeCN, r.t., 12 h; (c) Me S(O)I, NaH, DMSO, r.t., 13 h, 43% over three steps (ma- were followed by reduction with lithium aluminium deu- 3 jor diastereomer). teride (LAD) to afford dec-9-en-1-ol-1,1-d2 (10), which was transformed into the requisite aldehyde 11 via Swern oxidation. As we intend to employ mass spectrometry to analyse the results of our competitive kinetic isotope studies, we OH required a mass tag to differentiate products derived from a,b,c D-labelled isotopologues and unlabelled dihydrosterculic 20 D D acid. Accordingly, we prepared 1-iodooctane-8,8,8-d3 (15) OH from 1,8-octanediol (Scheme 4). Monobenzylation was fol- 10 lowed by oxidation to the corresponding aldehyde. Szpli- d man’s protocol for 2,2,6,6-tetramethylpiperidine-1-oxyl O (TEMPO)-catalysed oxidation to the mixed anhydride and 21 D conversion into the isopropyl ester then provided facile 11 access to ester 14. Subsequent reduction with LAD, alcohol 22 Scheme 2 Reagents and conditions: (a) CrO3, aq H2SO4, acetone, tosylation, and tosylate reduction with LAD afforded the 0 °C→r.t., 20 h, 95%; (b) H SO (cat.), IPA, Δ, 18 h, 90%; (c) LAD, THF, 2 4 desired terminal CD3 group. Hydrogenolysis with Pearl- r.t., 1 h, 96%; (d) [ClC(O)]2, DMSO, TEA, CH2Cl2, –78 °C, 1 h, 81%. man’s catalyst, followed by Appel iodination produced the desired iodide 15 in high yield. Addition of the anion of 9 to 11 afforded the desired alcohol 12 as a mixture of alcohol epimers and a minor amount of alkene 13 (Scheme 3). Excess aldehyde was re- Georg Thieme Verlag Stuttgart · New York — SynOpen 2018, 2, 168–175 170 Syn Open S. W. Shields et al. Paper OH The lithium-sulfoxide exchange/alkylation of 5 proceed- HO ed in the expected moderate yield (Scheme 6). The subse- a,b,c O quent lithium-sulfoxide exchange/deuteration of 18 afford- OBn ed some surprising results. Unlike the lithium-sulfoxide ex- O 14 change reaction of 5, the reaction of 18 with t-BuLi produces an intermediate cyclopropyllithium species 19 d,e,f,g,h that lacks the stabilisation afforded by a residual sulfoxide 23 D3C I group. Accordingly, the more reactive t-BuLi was used and 15 t-butyl p-tolyl sulfoxide (20) was formed as a byproduct. Scheme 4 Reagents and conditions: (a) NaH, BnBr, THF/DMF, 0 °C to r.t., This sulfoxide lacks acidic protons on the α carbon; never- 18 h, 51%; (b) TEMPO (1 mol%), KBr (10 mol%), NaOCl, CH2Cl2, pH 8.6 theless, when 18 was allowed to stir for 10 minutes at buffer, 0 °C, 0.5 h, 99%; (c) TEMPO (5 mol%), pivalic acid, t-BuOCl, pyr., –78 °C after a slow addition of t-BuLi followed by the addi- MeCN, 0 °C, then IPA, DIPEA, DMAP, r.t., 18 h, 91%; (d) LAD, THF, 0 °C to tion of a large excess of MeOD, we observed less than 5% D r.t., 6 h, 84%; (e) TsCl, TEA, Me N·HCl (10 mol%), toluene, 0 °C, 1 h, 89%; 3 incorporation on the cyclopropane ring. We hypothesise (f) LAD, THF, 0 °C to r.t., 2.5 h, 77%; (g) H (1 atm.), cat. Pd(OH) /C, EtO- 2 2 that even at –78 °C, cyclopropyllithium 19 rapidly depro- Ac, r.t., 48 h, 98%; (h) Ph3P, I 2, imidazole, CH2Cl2, 0 °C to r.t., 0.5 h, 96%.
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