Meyer–Schuster rearrangement
| Meyer–Schuster rearrangement | |
|---|---|
| Named after | Kurt Heinrich Meyer Kurt Schuster |
| Reaction type | Rearrangement reaction |
| Identifiers | |
| RSC ontology ID | RXNO:0000476 |
The Meyer–Schuster rearrangement is the chemical reaction described as an acid-catalyzed rearrangement of secondary and tertiary propargyl alcohols to α,β-unsaturated ketones if the alkyne group is internal and α,β-unsaturated aldehydes if the alkyne group is terminal.[1][2][3][4]
Mechanism
[edit]
The reaction proceeds by three major steps: (1) the rapid protonation of oxygen, (2) the slow, rate-determining step comprising the 1,3-shift of the protonated hydroxy group, and (3) the keto-enol tautomerism followed by rapid deprotonation.[5] Formation of the unsaturated carbonyl compound is irreversible.[6] Solvent is important and solvent caging is proposed to stabilize the transition state.[7]
Rupe rearrangement
[edit]The reaction of tertiary alcohols containing an α-acetylenic group does not produce the expected aldehydes, but rather α,β-unsaturated methyl ketones via an enyne intermediate.[8][9] This alternate reaction is called the Rupe reaction, and competes with the Meyer–Schuster rearrangement in the case of tertiary alcohols.
Use of catalysts
[edit]The traditional Meyer–Schuster rearrangement is induced by strong acids, which introduces competition with the Rupe reaction if the alcohol is tertiary.[1] Milder conditions are possible with transition metal-based and Lewis acid catalysts (for example, Ru-[10] and Ag-based[11] catalysts). Microwave-radiation with InCl3 catalyst to give excellent yields with short reaction times and good stereoselectivity.[12]
Use in organic synthesis
[edit]The Meyer–Schuster rearrangement has been used in several syntheses. ω-Alkynyl-ω-carbinol lactams convert into enamides using catalytic PTSA[13] α,β-Uunsaturated thioesters have been prepared from γ-sulfur substituted propargyl alcohols.[14] 3-Alkynyl-3-hydroxyl-1H-isoindoles rearrange under mildly acidic conditions to the α,β-unsaturated carbonyl compounds.[15] The synthesis of a part of paclitaxel exploits this rearrangement for a diastereomerically-selective route to the E-alkene.[16]
The step shown above had a 70% yield (91% when the byproduct was converted to the Meyer-Schuster product in another step). The authors used the Meyer–Schuster rearrangement because they wanted to convert a hindered ketone to an alkene without destroying the rest of their molecule.
History
[edit]The reaction is named after Kurt Meyer and Kurt Schuster.[17] Reviews have been published by Swaminathan and Narayan,
References
[edit]- ^ a b Swaminathan, S.; Narayan, K. V. "The Rupe and Meyer-Schuster Rearrangements" Chem. Rev. 1971, 71, 429–438. (Review)
- ^ Vartanyan, S. A.; Banbanyan, S. O. Russ. Chem. Rev. 1967, 36, 670. (Review)
- ^ Engel, D.A.; Dudley, G.B. Organic and Biomolecular Chemistry 2009, 7, 4149–4158. (Review)
- ^ Li, J.J. In Meyer-Schuster rearrangement; Name Reactions: A Collection of Detailed Reaction Mechanisms; Springer: Berlin, 2006; pp 380–381.(doi:10.1007/978-3-642-01053-8_159)
- ^ Edens, M.; Boerner, D.; Chase, C. R.; Nass, D.; Schiavelli, M. D. J. Org. Chem. 1977, 42, 3403–3408. (doi:10.1021/jo00441a017)
- ^ Andres, J.; Cardenas, R.; Silla, E.; Tapia, O. J. Am. Chem. Soc. 1988, 110, 666–674. (doi:10.1021/ja00211a002)
- ^ Tapia, O.; Lluch, J.M.; Cardena, R.; Andres, J. J. Am. Chem. Soc. 1989, 111, 829–835. (doi:10.1021/ja00185a007)
- ^ Rupe, H.; Kambli, E. Helv. Chim. Acta 1926, 9, 672. (doi:10.1002/hlca.19260090185)
- ^ Li, J.J. In Rupe rearrangement; Name Reactions: A Collection of Detailed Reaction Mechanisms; Springer: Berlin, 2006; pp 513–514.(doi:10.1007/978-3-642-01053-8_224)
- ^ Cadierno, V.; Crochet, P.; Gimeno, J. Synlett 2008, 1105–1124. (doi:10.1055/s-2008-1072593)
- ^ Sugawara, Y.; Yamada, W.; Yoshida, S.; Ikeno, T.; Yamada, T. J. Am. Chem. Soc. 2007, 129, 12902-12903. (doi:10.1021/ja074350y)
- ^ Cadierno, V.; Francos, J.; Gimeno, J. Tetrahedron Lett. 2009, 50, 4773–4776.(doi:10.1016/j.tetlet.2009.06.040)
- ^ Chihab-Eddine, Abderrahim; Jilale, Abderrahim; Daïch, Adam; Decroix, Bernard (2000). "Reactivity of N -benzyl-3-nitrophthalimide: A facile access to isoindolo[1,2- d ][3,5]benzothiazocine derivatives". Journal of Heterocyclic Chemistry. 37 (6): 1543–1548. doi:10.1002/jhet.5570370622.)
- ^ Yoshimatsu, Mitsuhiro; Naito, Motoyo; Kawahigashi, Masataka; Shimizu, Hiroshi; Kataoka, Tadashi (1995). "Meyer-Schuster Rearrangement of .gamma.-Sulfur-Substituted Propargyl Alcohols: A Convenient Synthesis of .alpha.,.beta.-Unsaturated Thioesters". The Journal of Organic Chemistry. 60 (15): 4798–4802. doi:10.1021/jo00120a024.)
- ^ Omar, Enouri A.; Tu, Chi; Wigal, Carl T.; Braun, Loren L. (1992). "The meyer-schuster rearrangement and hydrohalide addition of 3-alkynyl-3-hydroxy-1 H -isoindol-1-ones". Journal of Heterocyclic Chemistry. 29 (4): 947–951. doi:10.1002/jhet.5570290445.)
- ^ Crich, David; Natarajan, Swaminathan; Crich, Joyce Z. (1997). "Synthesis of the taxol AB-system by olefination of an A-ring C1 ketone and direct B-ring closure". Tetrahedron. 53 (21): 7139–7158. doi:10.1016/S0040-4020(97)00411-0.)
- ^ Meyer, Kurt H.; Schuster, Kurt (1922). "Umlagerung tertiärer Äthinyl-carbinole in ungesättigte Ketone". Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 55 (4): 819–823. doi:10.1002/cber.19220550403.)