Diastereoselective Diels–Alder Reactions of 1,7,9-Decatrien-3-ones to Highly Substituted Octalin Derivatives

Abstract

Based on an efficient synthesis of 1,7,9-decatrien-3-one precursors we studied their thermal and Lewis acid-promoted intramolecular Diels–Alder reactions to octalin derivatives. Whereas the thermal cycloadditions showed only cis/trans selectivities close to 35:65, the transformations were strongly influenced by the type of Lewis acid employed. With mono-coordinating Lewis acids such as BF₃, cis/trans ratios of up to 85:15 were observed, whereas di-coordinating Lewis acids such as TiCl₂(OiPr)₂ induce fairly high trans-selectivity. This remarkable switch of diastereoselectivity is discussed.

Key words

Diels–Alder reaction - intramolecular cycloaddition - Lewis acid - diastereoselectivity - titanium

• References

• 1 Thiemermann J, Andrä MS, Schnaubelt J, Lentz D, Zimmer R, Reissig H.-U. Synthesis 2016; DOI: 10.1055/s-0035-1562724.
• 2a Zschiesche R, Grimm EL, Reissig H.-U. Angew. Chem. Int. Ed. Engl. 1986; 25: 1086 ; Angew. Chem. 1986, 98, 1104
• 2b Zschiesche R, Frey B, Grimm E, Reissig H.-U. Chem. Ber. 1990; 123: 363
• 2c Frey B, Hünig S, Koch M, Reissig H.-U. Synlett 1991; 854
• 2d Schnaubelt J, Reissig H.-U. Synlett 1995; 452
• 2e Frey B, Schnaubelt J, Reissig H.-U. Eur. J. Org. Chem. 1999; 1377
• 2f Frey B, Schnaubelt J, Reissig H.-U. Eur. J. Org. Chem. 1999; 1385
• 2g Schnaubelt J, Frey B, Reissig H.-U. Helv. Chim. Acta 1999; 82: 666
• 2h Frey B, Reissig H.-U. J. Prakt. Chem. 1999; 341: 173

Reviews:
• 3a Brieger G, Bennett JN. Chem. Rev. 1980; 80: 63
• 3b Fallis AG. Can. J. Chem. 1984; 62: 183
• 3c Craig D. Chem. Soc. Rev. 1987; 16: 187
• 3d Roush WR. Intramolecular Diels–Alder Reactions . In Comprehensive Organic Synthesis . Vol. 5. Trost BM, Fleming I. Pergamon Press; Oxford: 1991: 513
• 3e Fallis AG. Acc. Chem. Res. 1999; 32: 464

Reviews:
• 4a Takao K, Munakata R, Tadano K. Chem. Rev. 2005; 105: 4779
• 4b Juhl M, Tanner D. Chem. Soc. Rev. 2009; 38: 2983
• 4c Heravi MM, Vavsari VF. RSC Adv. 2015; 5: 50890
• 5 Sustmann R. Pure Appl. Chem. 1974; 40: 569
• 6 Andrä M. S.; Thiemermann J.; Schnaubelt J.; Lentz D.; Zimmer R.; Reissig H.-U. Eur. J. Org. Chem. submitted.
• 7 Mayr H, Ofial A. Angew. Chem. Int. Ed. 2006; 45: 1844 ; Angew. Chem. 2006, 118, 1876

For a detailed interpretation, see:
• 8a Coe JW, Roush WR. J. Org. Chem. 1989; 54: 915

For additional examples, see:
• 8b Taber DF, Gunn BP. J. Am. Chem. Soc. 1979; 101: 3992
• 8c Corey EJ, Magriotis PA. J. Am. Chem. Soc. 1987; 109: 287
• 8d Van Royen LA, Mingheer R, De Clercq PJ. Tetrahedron 1985; 41: 4667
• 8e Fischer K, Hünig S, Öller M. Chem. Ber. 1986; 119: 3783
• 8f Golden JE, Aubé J. Angew. Chem. Int. Ed. 2002; 41: 4316 ; Angew. Chem. 2002, 114, 4492
• 8g Dineen TA, Roush WR. Org. Lett. 2005; 7: 1355

For recent discussions of the endo rule, see:
• 9a Kong S, Evanseck JD. J. Am. Chem. Soc. 2000; 122: 10418
• 9b García JI, Mayoral JA, Salvatella L. Eur. J. Org. Chem. 2005; 85
• 9c Yan S, Ryu DH, Lee JY. Bull. Korean Chem. Soc. 2010; 31: 2527
• 9d Fernández I, Bickelhaupt FM. J. Comput. Chem. 2014; 35: 371
• 10 Yamamoto H, Maruoka K, Imoto H. J. Am. Chem. Soc. 1990; 31: 12115
• 11 Since the mass balance was only moderate in this experiment we cannot rigorously exclude the formation of cis-8.

For X-ray crystal structure analyses, see:
• 12a Poll T, Metter JO, Helmchen G. Angew. Chem. Int. Ed. Engl. 1985; 24: 112 ; Angew. Chem. 1985, 97, 116
• 12b Viars B, Poulin M, Grandjean D, Anandrut J. J. Chem. Res., Synop. 1983; 84
• 12c Utko J, Soboza P, Lis T. J. Organomet. Chem. 1987; 334: 341

For selected publications describing reactions and structures of titanium chelate complexes:
• 12d Mikami K, Terada M, Motoyama Y, Nakai T. Tetrahedron: Asymmetry 1991; 2: 643
• 12e Duthaler RO, Hafner A. Chem. Rev. 1992; 92: 807
• 12f Carreira EM, Singer RA, Lee WS. J. Am. Chem. Soc. 1994; 116: 8837
• 12g Seebach D, Dahinden R, Marti RE, Beck AK, Plattner DA, Kühnle FN. M. J. Org. Chem. 1995; 60: 1788
• 12h Evans DA, Kozlowski MC, Tedrow JS. Tetrahedron Lett. 1996; 37: 7481
• 12i Fric H, Kogler FR, Puchberger M, Schubert U. Z. Naturforsch., B 2004; 59: 1241
• 12j Ketterer NA, Ziller JW, Rheingold AL, Heyduk AF. Organometallics 2007; 26: 5330
• 12k Immel TA, Grützke M, Späte A.-K, Groth U, Öhlschläger P, Huhn T. Chem. Commun. 2012; 48: 5790
• 12l Ryken SA, Schafer LL. Acc. Chem. Res. 2015; 48: 2576

For diastereoselective nucleophilic additions involving similar seven-membered ring chelates, see:
• 13a Janowitz A, Kunz T, Handke G, Reissig H.-U. Synlett 1989; 24
• 13b Kunz T, Janowitz A, Reissig H.-U. Chem. Ber. 1989; 122: 2165
• 13c Angert H, Kunz T, Reissig H.-U. Tetrahedron 1992; 48: 5681
• 13d Angert H, Reissig H.-U. J. Org. Chem. 1993; 58: 6280
• 13e Angert H, Schumacher R, Reissig H.-U. Chem. Ber. 1996; 129: 227 ; and references cited
• 14 The Lewis acids may also coordinate to the two alkoxycarbonyl groups of the precursor compounds; however, in equilibrium the seven-membered ring chelate should also be present.
• 15a For a review on the coordination of Lewis acids to carbonyl groups, see: Shambayati S, Growe WE, Schreiber SL. Angew. Chem. Int. Ed. Engl. 1990; 29: 256 ; Angew. Chem. 1990, 102, 273
• 15b For a theoretical study, see: Jonas V, Frenking G, Reetz MT. J. Am. Chem. Soc. 1994; 116: 8741
• 16a Denmark SE, Almstead NG. Tetrahedron 1992; 48: 5565
• 16b Walter MA, Heathcock CH. J. Org. Chem. 1991; 56: 5747
• 17 Rogers C, Keay BA. Can. J. Chem. 1992; 70: 2929 ; and literature cited

For similar strong effects on the diastereoselectivity of hetero-Diels–Alder reactions, see:
• 18a Tietze LF, Schneider C. Synlett 1992; 755
• 18b Tietze LF, Schneider C, Montenbruck A. Angew. Chem. Int. Ed. Engl. 1994; 33: 980 ; Angew. Chem. 1994, 106, 1031
• 18c Tietze LF, Schulz G. Liebigs Ann. 1995; 1921

For recent total syntheses, see:
• 19a Burke LT, Dixon DJ, Ley SV, Rodriguez F. Org. Biomol. Chem. 2005; 3: 274
• 19b Yin J, Kong LL, Wang C, Shi YB, Cai SJ, Gao SH. Chem. Eur. J. 2013; 19: 13040 ; and references cited