Organocatalytic Stereoisomerization versus Alkene Isomerization: Catalytic Asymmetric Synthesis of 1-Hydroxy-trans-2,5-diphenylphospholane 1-Oxide

Lukas Hintermann; Marco Schmitz; Oleg V. Maltsev; Panče Naumov

doi:10.1055/s-0032-1316835

Synthesis, Table of Contents

Synthesis 2013; 45(3): 308-325
DOI: 10.1055/s-0032-1316835

feature article

Organocatalytic Stereoisomerization versus Alkene Isomerization: Catalytic Asymmetric Synthesis of 1-Hydroxy-trans-2,5-diphenylphospholane 1-Oxide

Lukas Hintermann*

^aDepartment Chemie, Technische Universität München, Lichtenbergstr. 4, 85748 Garching bei München, Germany Fax: +49(89)28913669 Email: lukas.hintermann@tum.de

,

Marco Schmitz

^aDepartment Chemie, Technische Universität München, Lichtenbergstr. 4, 85748 Garching bei München, Germany Fax: +49(89)28913669 Email: lukas.hintermann@tum.de

,

Oleg V. Maltsev

^aDepartment Chemie, Technische Universität München, Lichtenbergstr. 4, 85748 Garching bei München, Germany Fax: +49(89)28913669 Email: lukas.hintermann@tum.de

,

Panče Naumov

^bNew York University Abu Dhabi, PO Box 129188, Abu Dhabi, UAE

^cInstitute for Chemical Research and the Hakubi Center for Advanced Research, Kyoto University, Uji, Kyoto 611–0011, Japan

› Author Affiliations

Abstract

All articles of this category

Abstract

The potential for an organocatalytic asymmetric stereoisomerization or alkene isomerization as atom-economic reaction with minimal structural change was investigated. The McCormack cycloaddition of 1,4-diarylbuta-1,3-dienes with (dialkylamino)dichlorophosphane and aluminum trichloride gives meso-2,5-diaryl-1-(dialkylamino)-1-oxo-2,5-dihydro-1H-phospholes, which were identified as suitable substrates for asymmetric isomerization to (1R,5R)-2,5-diaryl-1-(dialkylamino)-1-oxo-4,5-dihydro-1H-phospholes in the presence of bifunctional organocatalysts (cinchona alkaloids, Takemoto catalyst) in up to 91% ee and quantitative yield. The substrate range and the mechanism of the catalysis were studied. The reaction involves proton abstraction by the base, but a primary deuterium KIE is absent. Enriched (1R,5R)-1-(diethylamino)-1-oxo-2,5-diphenyl-4,5-dihydro-1H-phosphole was hydrolyzed to (5R)-1-hydroxy-1-oxo-2,5-diphenyl-4,5-dihydro-1H-phosphole, which was hydrogenated diastereoselectively under dissolving metal conditions to give (2R,5R)-1-hydroxy-1-oxo-2,5-diphenylphospholane (Fiaud’s acid) in preference to meso-1-hydroxy-1-oxo-2,5-diphenylphospholane. An asymmetric catalytic total synthesis of Fiaud’s acid, which is a building block for chiral phospholane synthesis, has been realized in five steps from thiophene, using nickel-catalyzed Wenkert arylation, McCormack cycloaddition, asymmetric dihydro-1H-phosphole isomerization, hydrolysis, and diastereoselective hydrogenation.

Key words

asymmetric catalysis - isomerization - heterocycles - phosphorus - stereoselective synthesis

Full Text

References

References
1 This definition of isomerization encompasses stereoiso-merizations and tautomerization (bond order isomerization), but not rearrangements, in order to point out the minimal change to the substrate in the course of the reaction.

2a Larsen CR, Grotjahn DB. J. Am. Chem. Soc. 2012; 134: 10357
2b Frauenrath H, Brethauer D, Reim S, Maurer M, Raabe G. Angew. Chem. Int. Ed. 2001; 40: 177
2c Fu G In Modern Rhodium-Catalyzed Organic Reactions . Evans PA. Wiley-VCH; Weinheim: 2005
2d Akutagawa S. Top. Catal. 1997; 4: 271
2e Otsuka S, Tani K. Synthesis 1991; 665

3a Mantilli L, Mazet C. Chem. Lett. 2010; 40: 341
3b Uma R, Crévisy C, Grée R. Chem. Rev. 2003; 103: 27
3c Van der Drift RC, Bouwman E, Drent E. J. Organomet. Chem. 2002; 650: 1

4a Inoue S, Takaya H, Tani K, Otsuka S, Sato T, Noyori R. J. Am. Chem. Soc. 1990; 112: 4897
4b Tani K, Yamagata T, Akutagawa S, Kumobayashi H, Taketomi T, Takaya H, Miyashita A, Noyori R, Otsuka S. J. Am. Chem. Soc. 1984; 106: 5208

5 Olah GA, Molnár A. Hydrocarbon Chemistry . 2nd ed Wiley Interscience; New York: 2003: 177

For related asymmetric organocatalytic alkyne/allene isomerization reactions:

6a Liu H, Leow D, Huang K.-W, Tan C.-H. J. Am. Chem. Soc. 2009; 131: 7212
6b Oku M, Arai S, Katayama K, Shioiri T. Synlett 2000; 493
6c Inokuma T, Furukawa M, Suzuki Y, Kimachi T, Kobayashi Y, Takemoto Y. ChemCatChem 2012; 4: 983
6d Jacobs TL, Dankner D. J. Org. Chem. 1957; 22: 1424

7 A classic example would be the conversion of tartaric acid into mixtures containing meso- and rac-tartaric acid by heating in water at 170 °C: Pasteur L. C. R. Hebd. Seances Acad. Sci. 1852; 35: 176

For a discussion of the feasibility of asymmetric catalysis of equilibrium reactions, see:

8a Hintermann L In Asymmetric Synthesis — More Methods and Applications . Christmann M, Bräse S. Wiley-VCH; Weinheim: 2012: 109
8b Hintermann L, Dittmer C. Eur. J. Org. Chem. 2012; 5573

9 Japp FR, Moir J. J. Chem. Soc., Trans. 1900; 608
10 Williams OF, Bailar JC. J. Am. Chem. Soc. 1959; 81: 4464
11 Isomerization of amarine to isoamarine requires excess NaOH in ethylene glycol at 155 °C.¹⁰ Attempted isomerization of N-tosyl-amarine with cinchona alkaloids was not successful (Hintermann, L., unpublished result). The approach is pointless for free amarine, since isoamarine racemizes under relatively mild conditions: Busacca CA, Bartholomeyzik T, Cheekoori S, Grinberg N, Lee H, Ma S, Saha A, Shen S, Senanayake CH. J. Org. Chem. 2008; 73: 9756

12a Guillen F, Fiaud J.-C. Tetrahedron Lett. 1999; 40: 2939
12b Guillen F, Rivard M, Toffano M, Legros J.-Y, Daran J.-C, Fiaud J.-C. Tetrahedron 2002; 58: 5895
12c Fiaud J.-C, Legros J.-Y. Tetrahedron Lett. 1991; 32: 5089

A stoichiometric asymmetric protonation approach to the isomerization of 2 to 3 had already been reported:

13a Guillen F, Moinet C, Fiaud J.-C. Bull. Soc. Chim. Fr. 1997; 134: 371
13b For a related asymmetric alkylation approach: Blake AJ, Hume SC, Li W.-S, Simpkins NS. Tetrahedron 2002; 58: 4589

14 Hintermann L, Schmitz M. Adv. Synth. Catal. 2008; 350: 1469
15 Wu Y, Singh RP, Deng L. J. Am. Chem. Soc. 2011; 133: 12458
16 Hintermann L, Schmitz M, Chen Y. Adv. Synth. Catal. 2010; 352: 2411

17a McCormack WB. US 2663737, 1953
17b McCormack WB. Org. Synth. 1963; 43: 73

18a Campbell IG. M, Cookson RC, Hocking MB, Hughes AN. J. Chem. Soc. 1965; 2184
18b Ezzell BR, Freedman LD. J. Org. Chem. 1970; 35: 241
18c Lukas B, Roberts RM. G, Silver J, Wells AS. J. Organomet. Chem. 1983; 256: 103

19a Cowley AH, Kemp RA, Lasch JG, Norman NC, Stewart CA. J. Am. Chem. Soc. 1983; 105: 7444
19b Cowley AH, Kemp RA, Lasch JG, Norman NC, Stewart CA, Whittlesey BR, Wright TC. Inorg. Chem. 1986; 25: 740
19c SooHoo CK, Baxter SG. J. Am. Chem. Soc. 1983; 105: 7443
19d Polniaszek RP. J. Org. Chem. 1982; 57: 5189

20a King RB, Sadanani ND. Synth. React. Inorg. Met.-Org. Chem. 1985; 15: 149
20b Issleib K, Seidel W. Chem. Ber. 1959; 92: 2681

21 In this abbreviated nomenclature for cyclic compounds, cis and trans indicate the relative position of the aryl group at C2 and/or C5 to the central oxo-substituent at phosphorus, which is of higher priority than the amino group.
22 The crystal structures have been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition numbers CCDC 901663 (8d) and 901662 (9d).
23 Bodalski R, Janecki T, Galdecki Z, Glowka ML. Phosphorus Sulfur Relat. Elem. 1982; 14: 15
24 Pakulski Z, Koprowski M, Pietrusiewicz M. Tetrahedron 2003; 59: 8219

25a Wang G.-W, Lu Q.-Q, Xia J.-J. Eur. J. Org. Chem. 2011; 4429
25b Seiser T, Cramer N. Chem. Eur. J. 2010; 16: 3383
25c Smith AB, Kingery-Wood J, Leenay TL, Nolen EG, Sunazuka T. J. Am. Chem. Soc. 1992; 114: 1438
25d Wenkert E, Greenberg RS, Kim H.-S. Helv. Chim. Acta 1987; 70: 2159
25e Carter MJ, Fleming I, Percival A. J. Chem. Soc., Perkin Trans. 1 1981; 2415
25f Alder K, Günzl-Schumacher M. Chem. Ber. 1959; 92: 822

26 Wenkert E, Leftin MH, Michelotti EL. J. Chem. Soc., Chem. Commun. 1984; 617

Precedence for base-mediated 2,5-dihydro-1H-phosphole to 4,5-dihydro-1H-phosphole rearrangements:

27a Keglevich G, Forintos H, Keseru GM, Hegedus L, Toke L. Tetrahedron 2000; 56: 4823
27b Tolmachev AA, Ivonin SP, Kharchenko AV, Lampeka RD, Kozlov ES. J. Gen. Chem. USSR (Engl. Transl.) 1991; 61: 852

28a Kappe O. Angew. Chem. Int. Ed. 2004; 43: 6250
28b Loupy A. Microwaves in Organic Synthesis . Wiley-VCH; Weinheim: 2002

29 Obermayer D, Gutmann B, Kappe CO. Angew. Chem. Int. Ed. 2009; 48: 8321
30 Hiemstra H, Wynberg H. J. Am. Chem. Soc. 1981; 103: 417

31a Connon SJ. Chem. Commun. 2008; 2499
31b Okino T, Hoashi Y, Takemoto Y. J. Am. Chem. Soc. 2003; 125: 12672

32 The NMR method of ee determination tends to underestimate enantioselectivity. Concerning the chiral HPLC analysis of 5b, see: Hintermann L. J. Org. Chem. 2007; 72: 9790
33 Pakulski Z, Demchuk OM, Kwiatosz R, Osinski PW, Swierczynska W, Pietrusiewicz KM. Tetrahedron: Asymmetry 2003; 14: 1459
34 Chadwick DJ, Willbe C. J. Chem. Soc., Perkin Trans. 1 1977; 887
35 See the Supporting Information for additional illustration or examples.
36 Westheimer F. Chem. Rev. 1961; 61: 265
37 Kresge AJ. Acc. Chem. Res. 1975; 8: 354

38a Duhaime RM, Weedon AC. J. Am. Chem. Soc. 1987; 109: 2479
38b Malhotra SK, Ringold HJ. J. Am. Chem. Soc. 1965; 87: 3228

39 Lampin JP, Mathey F, Bartet B. Bull. Soc. Chim. Fr. 1971; 317

40a Hols J, Gensow M.-N, Zayas O, Börner A. Curr. Org. Chem. 2007; 11: 61
40b Galland A, Paris JM, Schlama T, Guillot R, Fiaud J.-C, Toffano M. Eur. J. Org. Chem. 2007; 863
40c Pilkington CJ, Zanotti-Gerosa A. Org. Lett. 2003; 5: 1273
40d Jackson M, Lennon IC. Tetrahedron Lett. 2007; 48: 1831
40e Dobrota C, Toffano M, Fiaud J.-C. Tetrahedron Lett. 2004; 45: 8153
40f Fox ME, Jackson M, Lennon IC, Klosin J, Abboud KA. J. Org. Chem. 2008; 73: 775

41 Barton DH. R, Robinson CH. J. Chem. Soc. 1954; 3045
42 Polniaszek RP, Foster AL. J. Org. Chem. 1991; 56: 3137
43 For another NMR method of ee determination that also relies on the chirality of the sample itself, see: Feringa BL, Smaardijk A, Wynberg H. J. Am. Chem. Soc. 1985; 107: 4798
44 Nolde C, Schürmann M, Mehring M. Z. Anorg. Allg. Chem. 2007; 633: 142
45 Precedence: Suga T, Ohta S, Aoki T, Hirata T. Chem. Lett. 1985; 1331
46 In our communication,¹⁴ we stated in Scheme 3 that the signs of the optical rotation were the same in CH₂Cl₂ and MeOH solution. While this is true for 5b, 15b and 1, it is wrong for 19. The same scheme also gave the wrong sign of rotation for Fiaud’s acid 1; the enantiomer (2R,5R)-1 is dextro-rotatory in both MeOH (this work) and CH₂Cl₂.^12b The configurational assignments in that paper are not affected by these errors
47 Love BE, Jones EG. J. Org. Chem. 1999; 64: 3755
48 Hintermann L. Beilstein J. Org. Chem. 2007; 3: 22
49 Maerkl G, Alig B. J. Organomet. Chem. 1984; 273: 1
50 Obtained by hydrogenation of 4b over Pd/C with H₂ (g), compare with ref. 12b.
51 Hum G, Wooler K, Lee J, Taylor SD. Can. J. Chem. 2000; 78: 642

Supplementary Material

Supporting Information