Formation of Carbon Quaternary Stereogenic Center in Acyclic Systems via a Sequence of Carbometalation–Intramolecular Cyclization–Silicon Activation

Dedicated to the memory of Jean Normant, a wonderful teacher and truly inspirational colleague

Abstract

The diastereoselective carbometalation reaction of cyclopropenyl esters followed by reaction with acylsilanes provides γ-silylated lactones that undergo a ‘sila-Grob’ fragmentation to give pyrone enolates as a new source of acyclic δ-diketones, δ-keto acid, and δ-keto ester derivatives possessing a quaternary stereocenter.

Key words

quaternary carbon stereocenters - carbometalation - cyclopropenes - silicon activation - fragmentation

• References

• 1 Carreira EM, Kvaerno L. Classics in Stereoselective Synthesis . Wiley-VCH; Weinheim: 2009

For reviews published in 2014, see:
• 2a Volla CM. R, Atodiresei I, Rueping M. Chem. Rev. 2014; 114: 2390
• 2b Rotstein BH, Zaretsky S, Rai V, Yudin AK. Chem. Rev. 2014; 114: 8323
• 2c Cioc RC, Ruijter E, Orru RV. A. Green Chem. 2014; 16: 2958
• 2d Cho HY, Morken JP. Chem. Soc. Rev. 2014; 43: 4368

For reviews of quaternary carbon stereocenters, see:
• 3a Quasdorf KW, Overman LE. Nature (London) 2014; 516: 181
• 3b Hong AY, Stoltz BM. Eur. J. Org. Chem. 2013; 2745
• 3c Hawner C, Alexakis A. Chem. Commun. 2010; 46: 7295
• 3d Bella M, Casperi T. Synthesis 2009; 1583
• 3e Cozzi PG, Hilgraf R, Zimmermann N. Eur. J. Org. Chem. 2007; 5969
• 3f Trost BM, Jiang C. Synthesis 2006; 369
• 3g Denissova I, Barriault L. Tetrahedron 2003; 59: 10105
• 3h Christoffers J, Mann A. Angew. Chem. Int. Ed. 2001; 40: 4591
• 3i Corey EJ, Guzman-Perez A. Angew. Chem. Int. Ed. 1998; 37: 388

For reviews, see:
• 4a Eppe G, Didier D, Marek I. Chem. Rev. 2015; 115: 9175
• 4b Das JP, Marek I. Chem. Commun. 2011; 47: 4593
• 4c Marek I, Sklute G. Chem. Commun. 2007; 1683
• 5a Vasseur A, Perrin L, Eisenstein O, Marek I. Chem. Sci. 2015; 6: 2770
• 5b Masarwa A, Didier D, Zabrodski T, Schinkel M, Ackermann L, Marek I. Nature (London) 2014; 505: 199
• 6a Vabre R, Island B, Diehl CJ, Schreiner PR, Marek I. Angew. Chem. Int. Ed. 2015; 54: 9996
• 6b Pasco M, Gilboa N, Mejuch T, Marek I. Organometallics 2013; 32: 942
• 6c Mejuch T, Gilboa N, Gayon E, Wang H, Houk KN, Marek I. Acc. Chem. Res. 2013; 46: 1659
• 6d Mejuch T, Dutta B, Botoshansky M, Marek I. Org. Biomol. Chem. 2012; 10: 5803
• 6e Mejuch T, Botoshansky M, Marek I. Org. Lett. 2011; 13: 3604
• 6f Gilboa N, Wang H, Houk KN, Marek I. Chem. Eur. J. 2011; 17: 8000
• 6g Dutta B, Gilboa N, Marek I. J. Am. Chem. Soc. 2010; 132: 5588
• 6h Kolodney G, Sklute G, Perrone S, Knochel P, Marek I. Angew. Chem. Int. Ed. 2007; 46: 9291
• 6i Das JP, Chechik H, Marek I. Nat. Chem. 2009; 1: 128
• 6j Sklute G, Marek I. J. Am. Chem. Soc. 2006; 128: 4642
• 6k Marek I. Tetrahedron 2002; 58: 9463
• 7a Nairoukh Z, Marek I. Angew. Chem. Int. Ed. 2015; 54: 14393
• 7b Simaan M, Delaye P.-O, Shi M, Marek I. Angew. Chem. Int. Ed. 2015; 54: 12345
• 7c Minko Y, Marek I. Org. Biomol. Chem. 2014; 12: 1535
• 7d Minko Y, Pasco M, Lercher L, Marek I. Nat. Protoc. 2013; 8: 749
• 7e Minko Y, Pasco M, Botoshansky M, Marek I. Nature (London) 2012; 490: 522
• 7f Delaye P.-O, Didier D, Marek I. Angew. Chem. Int. Ed. 2013; 52: 5333
• 8 Marek I, Masarwa A, Delaye P.-O, Leibeling M. Angew. Chem. Int. Ed. 2015; 54: 414
• 9 Brook AG. Acc. Chem. Res. 1974; 7: 77
• 10 Zhang F.-G, Eppe G, Marek I. Angew. Chem. Int. Ed. 2016; 55: 714

For the enantioselective cyclopropenylation of alkynes, see:
• 11a Briones JF, Davies HM. L. J. Am. Chem. Soc. 2012; 134: 11916
• 11b Uehara M, Suematsu H, Yasutomi Y, Katsuki T. J. Am. Chem. Soc. 2011; 133: 170
• 11c Cui X, Xu X, Lu H, Zhu S, Wojitas L, Zhang XP. J. Am. Chem. Soc. 2011; 133: 3304
• 11d Goto K, Takeda K, Shiamda N, Nambu H, Anada M, Shiro M, Ando K, Hashimoto S. Angew. Chem. Int. Ed. 2011; 50: 6803
• 11e Briones JF, Davies HM. L. Tetrahedron 2011; 67: 4313
• 11f Briones JF, Hansen JH, Hardcastle KI, Autschbach J, Davies HM. L. J. Am. Chem. Soc. 2010; 132: 17211
• 11g Lou Y, Horikawa M, Kloster RA, Hawryluk NA, Corey EJ. J. Am. Chem. Soc. 2004; 126: 8916
• 12a Müller D, Marek I. Chem. Soc. Rev. 2016; in press; DOI: 10.1039/C5CS00897B
• 12b Didier D, Delaye P.-O, Simaan M, Island B, Eppe G, Eijsberg H, Kleiner A, Knochel P, Marek I. Chem. Eur. J. 2014; 20: 1038
• 12c Nakamura M, Isobe H, Nakamura E. Chem. Rev. 2003; 103: 1295
• 12d Fox JM, Yan N. Curr. Org. Chem. 2005; 9: 719
• 12e Rubin M, Rubina M, Gevorgyan V. Synthesis 2006; 1221
• 12f Rubin M, Rubina M, Gevorgyan V. Chem. Rev. 2007; 107: 3117
• 12g Zhu Z.-B, Wei Y, Shi M. Chem. Soc. Rev. 2011; 40: 5534
• 13a Smirnov P, Katan E, Mathew J, Kostenko A, Karni M, Nijs A, Bolm C, Marek I. J. Org. Chem. 2014; 79: 12122
• 13b Smirnov P, Mathew J, Nijs A, Katan E, Karni M, Bolm C, Marek I. Angew. Chem. Int. Ed. 2013; 52: 13717
• 13c Unger R, Cohen T, Marek I. Tetrahedron 2010; 66: 4874
• 13d Unger R, Cohen T, Marek I. Eur. J. Org. Chem. 2009; 1749
• 13e Unger R, Weisser F, Chinkov N, Stanger A, Cohen T, Marek I. Org. Lett. 2009; 11: 1853
• 14a Brook AG, Pascoe JD. J. Am. Chem. Soc. 1971; 93: 6224
• 14b Biernbaum MS, Mosher HS. J. Am. Chem. Soc. 1971; 93: 6221

For recent reviews on C–C cleavage, see:
• 15a Souillart L, Cramer N. Chem. Rev. 2015; 115: 9410
• 15b Souillart L, Parker E, Cramer N. Top. Curr. Chem. 2014; 346: 163
• 15c Ruhland K. Eur. J. Org. Chem. 2012; 2683
• 15d Aïssa C. Synthesis 2011; 3389
• 15e Murakami M, Matsuda T. Chem. Commun. 2011; 47: 1100
• 15f Masarwa A, Marek I. Chem. Eur. J. 2010; 16: 9712
• 16a Grob CA, Baumann W. Helv. Chim. Acta 1955; 38: 594
• 16b Drahl MA, Manpadi M, Williams LJ. Angew. Chem. Int. Ed. 2013; 52: 2
• 17a Chemler JA, Buchloz TJ, Geders TW, Akey DL, Rath CM, Chlipala GE, Smith JL, Sherman DH. J. Am. Chem. Soc. 2012; 134: 7359
• 17b Aoki Y, Matsumoto D, Kawaide H, Natsume M. J. Antibiot. (Tokyo) 2011; 64: 607
• 17c Chu M, Mierzwa R, Xu L, He L, Terracciano J, Patel M, Zhao W, Black TA, Chan TM. J. Antibiot. (Tokyo) 2002; 55: 215
• 17d Kong F, Singh MP, Carter GT. J. Nat. Prod. 2005; 68: 920
• 17e Brachmann AO, Brameyer S, Kresovic D, Hitkova I, Kopp Y, Manske C, Schubert K, Bode HB, Heerman R. Nat. Chem. Biol. 2013; 9: 573
• 18 Liao L.-A, Zhang F, Yan N, Golen JA, Fox JM. Tetrahedron 2004; 60: 1803
• 19 Danheiser RL, Fink DM, Okano K, Tsai YM, Szczepanski SW. J. Org. Chem. 1985; 50: 5393