Adventures in 1,1-Diphenylacetone Dianion Chemistry

Dedicated to Professor Dietmar Seyferth, in memoriam.

Abstract

The present personalized account highlights reactions of the dianion of 1,1-diphenylacetone and its applications. From a study directed towards the regioselectivity of such reactions a new allene synthesis via allene dianions was found by serendipity. In addition, reactions of allene dianions with various electrophiles have been studied.

1 Introduction

2 Cyclizations of the Dianion of 1,1-Diphenylacetone

2.1 Reaction with Bis(cyclopentadienyl)zirconium Dichloride

2.1 Reactions with Dichlorosilanes

2.1 Reactions with Difluorosilanes

2.1 Reactions with Ketones and Dielectrophiles

3 Regioselectivity of Dianion Reactions

4 Allene Dianions from Silyl Enol Ethers

5 Scope of the Reactions of Allene Dianions

6 Reactions of Allene Dianions with Ketones

7 Reactions of Allene Dianions with Nitriles

8 Conclusions

Keywords

allenes - cyclizations - dianions - silicon - silyl enol ethers

Publication History

Received: 24 November 2022

Accepted after revision: 04 December 2022

Article published online:
05 January 2023

• References

• 1a Trimitsis GB, Hinkley JM, TenBrink R, Poli M, Gustafson G, Erdman J, Rop D. J. Am. Chem. Soc. 1977; 99: 4838
• 1b Hubbard JS, Harris TM. J. Am. Chem. Soc. 1980; 102: 211
• 1c For a review, see: Langer P, Freiberg W. Chem. Rev. 2004; 104: 4125
• 1d Witt O, Mauser H, Friedl T, Wilhelm D, Clark T. J. Org. Chem. 1998; 63: 959
• 2 Seyferth D, Wang T, Davis WM. Organometallics 1994; 13: 4134
• 3 Seyferth D, Wang T, Langer P, Ostrander RL, Rheingold AL. Organometallics 1997; 16: 2413
• 4a Langer P, Döring M, Seyferth D. Synlett 1999; 135
• 4b Langer P, Döring M, Görls H. Eur. J. Org. Chem. 2001; 1511
• 5a Corey EJ, Rücker C. Tetrahedron Lett. 1984; 25: 4345
• 5b Brook AG, MacRae DM, Limburg WW. J. Am. Chem. Soc. 1967; 89: 5493
• 5c Brook AG. Acc. Chem. Res. 1974; 7: 77
• 6 Stork G, Hudrlik P. J. Am. Chem. Soc. 1968; 90: 4462
• 7 Greene TW, Wuts PG. M. Protective Groups in Organic Synthesis, 2nd ed. John Wiley & Sons; Hoboken: 1991: 68-87
• 8 Seyferth D, Langer P, Döring M. Organometallics 1995; 14: 4457
• 9 Bates RB, Kroposki IM, Potter DE. J. Org. Chem. 1972; 37: 560
• 10 Binger P, Müller P, Wenz R, Mynott R. Angew. Chem., Int. Ed. Engl. 1990; 29: 1037; Angew. Chem. 1990, 102, 1070
• 11 Negishi E, King AO, Klima WL, Patterson W, Silveira AJr. J. Org. Chem. 1980; 45: 2526
• 12 Brummond KM, Dingess EA, Kent JL. J. Org. Chem. 1996; 61: 6096
• 13a Naso F, Ronzini L. J. Chem. Soc., Perkin Trans. 1 1974; 340
• 13b Stang PJ, Hargrove RJ. J. Org. Chem. 1975; 40: 657
• 14 Langer P, Döring M, Seyferth D, Görls H. Chem. Eur. J. 2001; 7: 573
• 15 Grovenstein E, Chiu K.-W, Patil BB. J. Am. Chem. Soc. 1980; 102: 5848
• 16 Langer P. Chem. Commun. 1999; 1217
• 17 Langer P, Döring M, Seyferth D. Chem. Commun. 1998; 1927
• 18 Langer P, Seyferth D, Görls H. Eur. J. Org. Chem. 2003; 1948
• 19 Langer P, Freiberg W. Chem. Rev. 2004; 104: 4125
• 20 Langer P, Döring M. Eur. J. Org. Chem. 2002; 221
• 21 Dang TT, Dang TT, Langer P. Synlett 2011; 2633
• 22 Bellur E, Feist H, Langer P. Tetrahedron 2007; 63: 10865
• 23 Feist H, Langer P. Synthesis 2008; 3877
• 24 For a review of 1,3-bis(silyl enol ethers) in general, see: Langer P. Synthesis 2002; 441
• 25 Langer P. Synlett 2006; 3369
• 26 Feist H, Langer P. Synthesis 2007; 327
• 27 Langer P. Synlett 2007; 1016
• 28 Langer P. Eur. J. Org. Chem. 2007; 2233
• 29 Langer P. Synlett 2021; 32: 2036
• 30 For a review, see: Nawaz P, Sher M, Langer P. Synlett 2010; 2383
• 31 Langer P. Synlett 2009; 2205
• 32 Hassan Z, Langer P. Synlett 2019; 30: 665
• 33 Dang TT, Kelzhanova NK, Abilov ZA, Turmukhanova MZ, Langer P. Synlett 2012; 23: 1283