DABCO-Assisted Coupling of Some Activated Olefins and 2,3-Dihalo-1,4-naphthoquinones and Conversion to the Anthraquinone Derivatives

Abstract

A new synthesis of mono- and di-α-vinylnaphthoquinones based on stepwise or one-pot substitution of the halogens in 2,3-dihalo-1,4-naphthoquinones by DABCO-assisted enolate ion is described. Di-α-vinylnaphthoquinones undergo thermal 6π electrocyclization to yield 1,4-disubstituted anthraquinones readily.

Key words

Baylis-Hillman reaction - DABCO - 2,3-dihalo-1,4-naphthoquinone - activated olefin - anthraquinone

References

• For reviews of the Baylis-Hillman reaction, see:
• 1a Drewes SE. Roos GHP. Tetrahedron  1988,  44:  4653 
• 1b Basavaiah D. Rao PD. Hyma RS. Tetrahedron  1996,  52:  8001 
• 1c Ciganek E. In Organic Reactions   Vol. 51:  Paquette LA. Wiley; New York: 1997.  p.201 
• 1d Langer P. Angew. Chem. Int. Ed.  2000,  39:  3049 
• 1e Kim JN. Lee KY. Curr. Org. Chem.  2002,  6:  627 
• 1f Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 
• 2a Song YS. Lee CH. Lee K.-J. J. Heterocycl. Chem.  2003,  40:  939 
• 2b Lee CH. Song YS. Cho HI. Yang JW. Lee K.-J. J. Heterocycl. Chem.  2003,  40:  1103 
• For selected recent examples of Michael reaction under Baylis-Hillman reaction conditions, see:
• 3a Kaye PT. Nocanda XW. J. Chem. Soc., Perkin Trans. 1  2002,  1318 
• 3b Wang L.-C. Luis AL. Agapiou K. Jang H.-Y. Krische MJ. J. Am. Chem. Soc.  2002,  124:  2402 
• 3c Frank SA. Mergott DJ. Roush WR. J. Am. Chem. Soc.  2002,  124:  2404 
• 3d Drewes SE. Emslie ND. Korodia N. Synth. Commun.  1990,  20:  1915 
• 3e Basavaiah D. Gowriswari VVL. Bharathi TK. Tetrahedron Lett.  1987,  28:  4591 
• 4 For a Baylis-Hillman type reaction of 1,4-naphthoquinones with formalin, see: Bansal V. Sharma J. Khanna RN. J. Chem. Res., Synop  1998,  720 
• 5 Levin JI. Tetrahedron Lett.  1993,  34:  6211 
• 6a Berthiol F. Doucet H. Santelli M. Eur. J. Org. Chem.  2003,  1091 
• 6b Rossi R. Bellina F. Carpita A. Synlett  1996,  356 
• 7a Jalil AA. Kurono N. Tokuda M. Tetrahedron  2002,  58:  7477 
• 7b Aishah AJ. Kurono N. Tokuda M. Synlett  2001,  1944 
• 7c Jalil AA. Kurono N. Tokuda M. Synthesis  2002,  2681 
• 8a Finley KT. In The Chemistry of the Functional Groups, The Chemistry of the Quinonoid Compounds   Vol. 2:  Patai S. John Wiley & Sons; New York: 1974.  p.1047 
• 8b Smith LI. Austin FL. J. Am. Chem. Soc.  1942,  64:  528 
• 8c Reynolds GA. VanAllan JA. Adel RE. J. Org. Chem.  1965,  30:  3819 
• 8d Emadi A. Harwood JS. Kohanim S. Stagliano KW. Org. Lett.  2002,  4:  521 
• 8e Nesterova IN. Grinev AN. Rubtsov NM. Khim. Geterotsikl. Soedin.  1989,  66 ; Chem. Abstr. 1989, 111, 214358
• 8f Chaker L. Pautet F. Fillion H. Heterocycles  1995,  41:  1169 
• 10 For a previously reported synthesis of a similar compound by photochemical means, see: Naito T. Makita Y. Yazaki S. Kaneko C. Chem. Pharm. Bull.  1986,  34:  1505 
• 13 For previously reported synthesis of 6a, see: Alder K. Kuth R. Ann.  1957,  609:  19 
• 14a Miller AK. Trauner D. Angew. Chem. Int. Ed.  2003,  42:  549 
• 14b Beaudry CM. Trauner D. Org. Lett.  2002,  4:  2221 
• 14c Wang KK. Zhang Q. Liao J. Tetrahedron Lett.  1996,  37:  4087 
• 14d Okamura WH. Peter R. Reischl W. J. Am. Chem. Soc.  1985,  107:  1034 
• 14e Marvell EN. Caple G. Schatz B. Pippin W. Tetrahedron  1973,  29:  3781 
• 14f Marvell EN. Caple G. Delphey C. Platt J. Polston N. Tashiro J. Tetrahedron  1973,  29:  3797 
• 14g Vogel E. Grimme W. Dinné E. Tetrahedron Lett.  1965,  6:  391 
• 14h Marvell EN. Caple G. Schatz B. Tetrahedron Lett.  1965,  6:  385 

9

When employing 0.1 equivalent of DABCO, 2a was obtained in a 9% yield. No reaction or very low yields (5%) of 2a were produced using other tertiary amines (1.2 equiv) such as DMAP, DBU and DBN.

11

Unreacted 1b (13%) was recovered.

12

No reaction occurred in the case of acrolein.