It was 1973 when Mukaiyama and coworkers described the first application of silyl enol ethers in aldol additions.1 This reaction is promoted by Lewis acids and allowed a catalytic and an enantioselective execution for the first time.2 Moreover, the regioselectivity can be controlled efficiently by using defined silyl enol ether of unsymmetrical ketones. High chemoselectivities were observed by using aldehydes, ketones and carboxylic esters in these transformations (Scheme 3.1).3,4
The level and the sense of stereoselectivity often vary and depend on the aldehydes, silyl enol ethers and on the Lewis acids used. The stereochemical results have been rationalized by considering so-called open transitions states (Scheme 3.2).5 This illustration is a simple working model based on repulsive forces only. The influence of different Lewis acids, the influence of different substituents and the fate of silyl group during the reaction were not involved in this model. For further discussion and mechanistic understanding see Hiraiwa et al. and others.6
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References
Mukaiyama T, Narasaka K, Banno K (1973) Chem Lett 1011
Mukaiyama T, Banno K, Narasaka K (1974) J Am Chem Soc 96:7503
Banno K, Mukaiyama T (1975) Chem Lett 741
Banno K, Mukaiyama T (1976) Bull Chem Soc Jpn 49:2284
Murata S, Suzuki M, Noyori R (1980) J Am Chem Soc 102:3248
(a) Hiraiwa Y, Ishihara K, Yamamoto H (2006) Eur J Org Chem 1837; (b) Denmark SE, Lee W (2008) Chem Asian J 3:327;
Denmark SE, Lee W (2008) Chem Asian J 3
(c) Patel SG, Wiskur SL, (2009) Tetrahedron Lett 50:1164
(a) Yamamoto H, Ishihara K (eds) (2008) Acid Catalysis in Modern Organic Synthesis, Wiley, Weinheim;
(b) Yamamoto H (ed) (2000) Lewis Acids in Organic Synthesis, Wiley, Weinheim
Gennari C (1993) In: Comprehensive Organic Synthesis, Trost BM, Fleming I, Heathcock CH (eds). Pergamon, Oxford, vol 2, p 629
Braun W (1996) In: Houben-Weyl, Methoden der Organischen Chemie, Helmchen G, Hoffmann RW, Mulzer J, Schaumann E (eds). Thieme, Stuttgart, vol E21b, p 1603
Nelson SG (1998) Tetrahedron: Asymm 9:357
Mukaiyama T, Matsuo JI (2004) In: Modern Aldol Reactions, Mahrwald R (ed). Wiley-VCH, Weinheim, vol. 1, p 137
Carreira EM, Fettes A, Marti C (2006) Org Reactions 67:1
Kalesse M (2005) Top Curr Chem 244:43
Mukaiyama T (1999) Tetrahedron 55:8609
(a) Gröger H, Vogl EM, Shibasaki M (1998) Chem Eur J 4:1137;
(b) Johnson JS, Evans DA (2000) Acc Chem Res 33:325;
(c) Machajewski TD, Wong CH (2000) Angew Chem Int Ed 39:1352;
(d) Carreira EM (1999) In: Comprehensive Asymmetric Synthesis, Jacobsen EN, Pfaltz A, Yamamoto H (eds). Springer, Heidelberg, vol 3, p 998;
(e) Carreira EM (2000) In: Comprehensive Asymmetric Synthesis, 2nd edn, Ojima I (ed). Wiley-VCH, New York, p 513.
Alcaide B, Almendros P (2002) Eur J Org Chem 1595
(a) Doherty S, Goodrich P, Hardacre C, Parvulescu V, Paun C (2008) Adv Synth Cat 350:295;
(b) Fraile JM, Perez I, Mayoral JA (2007) J Cat 252:303;
(c) Costantino U, Fringuelli F, Nocchetti M, Piermatti O (2007) Appl Cat A 326:100;
(d) Gibson VC, Redshaw C, Solan GA (2007) Chem Rev 107:1745;
(e) Gu Y, Ogawa C, Kobayashi J, Mori Y, Kobayashi S (2006) Angew Chem Int Ed 45:7217;
(f) Fraile JM, Perez I, Mayoral JA, Reiser O (2006) Adv Synth Cat 348:1680
Mlynarski J, Paradowska J (2008) Chem Soc. Rev 37:1502
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(2009). Catalytic Aldol Additions. In: Mahrwald, R. (eds) Aldol Reactions. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8701-1_7
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