Exploration of Versatile Geminal Bis(silane) Chemistry

Abstract

Geminal bis(silyl) compounds, a special type of organosilane, are attractive synthons because of their great potential for bifunctional reactivity. This article outlines our recent efforts to develop a practical method to synthesize geminal bis(silane) compounds and to explore their interesting bifunctionality.

Key words

organosilane - geminal bis(silane) - bifunctional reactivity - silyl migration - Prins cyclization

• References and Notes


For selective reviews on organosilanes, see:
• 1a Overman LE, Blumenkopf TA. Chem. Rev. 1986; 86: 857
• 1b Panek M, Masse CE. Chem. Rev. 1995; 95: 1293
• 1c Langkopf E, Schinzer D. Chem. Rev. 1995; 95: 1375
• 1d Fleming I, Barbero A, Walter D. Chem. Rev. 1997; 97: 2063

For reviews on the Brook rearrangement, see:
• 2a Brook AG. Acc. Chem. Res. 1974; 7: 77
• 2b Moser WH. Tetrahedron 2001; 57: 2065
• 3a Danheiser RL, Carini DJ, Basak A. J. Am. Chem. Soc. 1981; 103: 1604
• 3b Danheiser RL, Kwasigroch CA, Tsai YM. J. Am. Chem. Soc. 1985; 107: 7233
• 3c Danheiser RL, Fink DM, Tsai YM. Org. Synth. 1988; 66: 8
• 3d Danheiser RL, Stoner EJ, Koyama H, Yamashita DS, Klade CA. J. Am. Chem. Soc. 1989; 111: 4407
• 3e Danheiser RL, Dixon BR, Gleason RW. J. Org. Chem. 1992; 57: 6094
• 4a Tamao K, Akita M, Kumada M. J. Organomet. Chem. 1983; 254: 13
• 4b Fleming I, Henning R, Plaut H. J. Chem. Soc., Chem. Commun. 1984; 29
• 4c For the latest review on Fleming–Tamao oxidation, see: Jones GR, Landais Y. Tetrahedron 1996; 52: 7599
• 5a Hatanaka Y, Hiyama T. J. Org. Chem. 1988; 53: 918
• 5b For the latest review on Hiyama coupling, see: Denmark S, Regens CS. Acc. Chem. Res. 2008; 41: 1486
• 6a Peterson DJ. J. Org. Chem. 1968; 33: 780
• 6b For the latest review on Peterson olefination, see: van Staden LF, Gravestock D, Ager DJ. Chem. Soc. Rev. 2002; 31: 195
• 7a Hosomi A, Endo M, Sakurai H. Chem. Lett. 1976; 941

For reviews on Sakurai allylation, see:
• 7b Fleming I. Allylsilanes, Allylstannanes and Related Systems . In Comp. Org. Synth. . Vol. 6. Trost BM, Fleming I. Pergamon Press; Oxford: 1991: 563-593
• 7c Schinzer D. Synthesis 1988; 263
• 7d Fleming I, Dunogues J, Smithers R. Org. React. 1989; 37: 57

For studies on geminal bis(silyl) species, see:
• 8a Fleming I, Floyd CD. J. Chem. Soc., Perkin Trans. 1 1981; 969
• 8b Ahlbrecht H, Farnung W, Simon H. Chem. Ber. 1984; 117: 2622
• 8c Brook AG, Chrusciel JJ. Organometallics 1984; 3: 1317
• 8d Klumpp GW, Mierop AJ. C, Vrielink JJ, Brugman A, Schakel M. J. Am. Chem. Soc. 1985; 107: 6740
• 8e Lautens M, Delanghe PH. M, Goh JB, Zhang CH. J. Org. Chem. 1995; 60: 4213
• 8f Lautens M, Ben RN, Delanghe PH. M. Tetrahedron 1996; 52: 7221
• 8g Princet B, Anselme G, Pornet J. Synth. Commun. 1999; 29: 3326
• 8h Princet B, Gariglio HG, Pornet J. J. Organomet. Chem. 2000; 604: 186
• 8i Hodgson DM, Barker SF, Mace LH, Moran JR. Chem. Commun. 2001; 153
• 8j Onyeozili EN, Maleczka RE. Tetrahedron Lett. 2006; 47: 6565

For reviews on geminal bimetallic species, see:
• 9a Marek I, Normant JF. Chem. Rev. 1996; 96: 3241
• 9b Marshall JA. Chem. Rev. 1996; 96: 31
• 9c Marek I. Chem. Rev. 2000; 100: 2887
• 10 Lautens M, Ben RN, Delanghe PH. M. Angew. Chem. Int. Ed. Engl. 1994; 33: 2448
• 11 Williams DR, Morales-Ramos ÁI, Williams CM. Org. Lett. 2006; 8: 4393

For recent studies on the retro-[1,4] Brook rearrangement, see:
• 12a Simpkins SM. E, Kariuki BM, Arico CS, Cox LR. Org. Lett. 2003; 5: 3971
• 12b Nahm MR, Xin LH, Potnick JR, Yates CM, White PS, Johnson JS. Angew. Chem. Int. Ed. 2005; 44: 2377
• 12c Yamago S, Fujita K, Miyoshi M, Kotani M, Yoshida J. Org. Lett. 2005; 7: 909
• 12d Mori H, Matsuo T, Yoshioka Y, Katsumura S. J. Org. Chem. 2006; 71: 9004
• 12e Mori Y, Futamura Y, Horisaki K. Angew. Chem. Int. Ed. 2008; 47: 1091
• 13a Mitchell TN, Schütze M, Giebelmann F. Synlett 1997; 187
• 13b Mitchell TN, Schütze M. Tetrahedron 1999; 55: 1285
• 14 Song ZL, Lei Z, Gao L, Wu X, Li LJ. Org. Lett. 2010; 12: 5298
• 15 Gao L, Lin XL, Lei J, Song ZL, Lin Z. Org. Lett. 2012; 14: 158

For reviews on anion relay chemistry (ARC), see:
• 16a Smith AB. III, Adams CM. Acc. Chem. Res. 2004; 37: 365
• 16b Smith AB. III, Wuest WM. Chem. Commun. 2008; 5883

For the latest advances, see:
• 16c Smith AB. III, Kim WS. Proc. Natl. Acad. Sci. U.S.A. 2011; 108: 6787
• 16d Smith AB. III, Tong RB, Kim WS, Maio WA. Angew. Chem. Int. Ed. 2011; 50: 8904
• 16e Smith AB. III, Han H, Kim WS. Org. Lett. 2011; 13: 3328
• 16f Smith AB. III, Hoye AT, Martinez-Solorio D, Kim W.-S, Tong RB. J. Am. Chem. Soc. 2012; 134: 4533
• 17 Sun XW, Lei J, Sun CZ, Song ZL, Yan LJ. Org. Lett. 2012; 14: 1094
• 18a Taguchi H, Ghoroku K, Tadaki M, Tsubouchi A, Takeda T. Org. Lett. 2001; 3: 3811
• 18b Smith AB. III, Kim WS, Tong RB. Org. Lett. 2010; 12: 588

For reviews on the bryostatins, see:
• 19a Hale KJ, Hummersone MG, Manaviazar S, Frigerio M. Nat. Prod. Rep. 2002; 19: 413
• 19b Kortmansky J, Schwartz GK. Cancer Invest. 2003; 21: 924
• 19c Wender PA, Baryza JL, Hilinski MK, Horan JC, Kan C, Verma VA. Beyond Natural Products: Synthetic Analogues of Bryostatin 1 . In Drug Discovery Research: New Frontiers in the Post-Genomic Era . Huang Z. Wiley-VCH; Weinheim: 2007: 127-162
• 19d Hale KJ, Manaviazar S. Chem.–Asian J. 2010; 5: 704
• 20 Lu J, Song ZL, Zhang YB, Gan ZB, Li HZ. Angew. Chem. Int. Ed. 2012; 51: 5367
• 21 For the latest review on Prins cyclization, see: Crane EA, Scheidt KA. Angew. Chem. Int. Ed. 2010; 49: 8316
• 22 The geminal bis(silyl) homoallylic alcohols 19 were synthesized in 55–60% yield by a zinc-promoted Barbier reaction of aldehyde with bis(silyl) allyl bromide, which was prepared from bis(silyl) enal 11 in three steps. See the Supporting Information of ref. 15 for details.