Design and Synthesis of Angularly Annulated Spirocyclics via Enyne Metathesis and the Diels–Alder Reaction as Key Steps

Abstract

We have developed a simple and an efficient route to a range of angularly fused spirocycles by the application of enyne metathesis and the Diels–Alder reaction as key steps. The enyne metathesis protocol has been further extended to the dibenzylation of indane-1,3-dione by using cross-enyne metathesis in the presence of hexa-1,5-diene with the aid of Grubbs’ 1st generation catalyst followed by an aromatization sequence with DDQ.

Key words

active methylene compounds - cross-metathesis - Diels–Alder reaction - enyne metathesis - spirocyclic compounds

• References

• 1a Grubbs RH. Tetrahedron 2004; 60: 7117
• 1b Fürstner A. Angew. Chem. Int. Ed. 2000; 39: 3013
• 1c Deiters A, Martin SF. Chem. Rev. 2004; 104: 2199
• 2a Holt DJ, Barker WD, Jenkins PR, Davies DL, Garratt S, Fawcett J, Russell DR, Ghosh S. Angew. Chem. Int. Ed. 1998; 37: 3298
• 2b Kotha S, Manivannan E, Sreenivasachary N, Ganesh T, Deb AC. Synlett 1999; 1618
• 2c Giessert AJ, Diver ST. Chem. Rev. 2004; 104: 1317
• 2d Maifeld SV, Lee D. Chem.–Eur. J. 2005; 11: 6118
• 2e Mori M. Adv. Synth. Catal. 2007; 349: 121
• 2f Kotha S, Mandal K. Chem. Asian J. 2009; 4: 354
• 2g Kotha S, Dipak MK. Tetrahedron 2012; 68: 397
• 2h Kotha S, Lahiri K. Synlett 2007; 2767
• 2i Kotha S, Sreenivasachary N. Indian J. Chem., Sect. B 2001; 40: 763
• 2j Ruprah PK, Cros J.-P, Pease JE, Whittingham WG, Williams JM. J. Eur. J. Org. Chem. 2002; 3145
• 2k Lee H.-Y, Kim BG, Snapper ML. Org. Lett. 2003; 5: 1855
• 3a Katz TJ, McGinnis J. J. Am. Chem. Soc. 1975; 97: 1592
• 3b Katz TJ, Sivavec TM. J. Am. Chem. Soc. 1985; 107: 737
• 3c Sivavec TM, Katz TJ, Chiang MY, Yang GX.-Q. Organometallics 1989; 8: 1620
• 3d Katz TJ, Yang GX.-Q. Tetrahedron Lett. 1991; 32: 5895
• 3e Kotha S, Meshram S, Tiwari A. Chem. Soc. Rev. 2009; 38: 2065
• 3f Kurhade SE, Sanchawala AI, Ravikumar V, Bhuniya D, Reddy DS. Org. Lett. 2011; 13: 3690
• 3g For one-pot metathesis/Diels–Alder reaction see: Lee H.-Y, Kim HY, Tae H, Kim BG, Lee J. Org. Lett. 2003; 5: 3439
• 3h Bentz D, Laschat S. Synthesis 2000; 1766
• 3i Banti D, North M. Tetrahedron Lett. 2002; 43: 1561
• 3j Guo H, Madhushaw RJ, Shen F.-M, Liu R.-S. Tetrahedron 2002; 58: 5627
• 3k Hoye TR, Donaldson SM, Vos TJ. Org. Lett. 1999; 1: 277

For the total synthesis of natural products by metathesis, see ref 3k and:
• 4a Boyer F.-D, Hanna I, Ricard L. Org. Lett. 2004; 6: 1817
• 4b Kinoshita A, Mori M. J. Org. Chem. 1996; 61: 8356
• 4c Kummer DA, Brenneman JB, Martin SF. Org. Lett. 2005; 7: 4621
• 4d Mori M, Tonogaki K, Nishiguchi N. J. Org. Chem. 2002; 67: 224
• 5 For all the four compounds shown in Figure 1, see: Mori M. Materials 2010; 3: 2087
• 6a Sannigrahi M. Tetrahedron 1999; 55: 9007
• 6b Holt DJ, Barker WD, Jenkins PR, Panda J, Ghosh S. J. Org. Chem. 2000; 65: 482
• 6c Kotha S. Acc. Chem. Res. 2003; 36: 342
• 6d Kotha S, Mandal K. Tetrahedron Lett. 2004; 45: 1391
• 6e Kotha S, Deb AC, Chattopadhyay S. Lett. Org. Chem. 2006; 3: 128
• 6f Kotha S, Deb AC, Lahiri L, Manivannan E. Synthesis 2009; 165
• 6g Kotha S, Dipak MK, Mobin SM. Tetrahedron 2011; 67: 4616
• 6h Kotha S, Deb AC. Indian J. Chem., Sect. B 2008; 47: 1120
• 6i Kotha S, Manivannan E. ARKIVOC 2003; iii: 67 ; http://www.arkat-usa.org/home
• 6j Kotha S, Deb AC, Kumar RV. Bioorg. Med. Chem. 2005; 15: 1039
• 6k Singh P, Paul K. J. Heterocycl. Chem. 2006; 43: 607
• 6l Basavaiah D, Badsara SS, Veeraraghavaiah G. Tetrahedron 2013; 69: 7995
• 6m Basavaiah D, Reddy KR. Org. Lett. 2007; 9: 57
• 6n Kozhushkov SI, de Meijere A, Haumann T, Boese R. Angew. Chem. Int. Ed. 1993; 32: 401
• 7a Mehta G, Subrahmanyam D. Tetrahedron 1987; 28: 479
• 7b Kelly TR, Ohashi N. J. Am. Chem. Soc. 1986; 108: 7100
• 7c Keese R. Chem. Rev. 2006; 106: 4787
• 7d Kuck D, Bögge H. J. Am. Chem. Soc. 1986; 108: 8107
• 8a Naik SN, Pandey B, Ayyangar NR. Synth. Commun. 1988; 633
• 8b Sakata Y, Goto S, Tatemitsu H, Misumi S. J. Am. Chem. Soc. 1989; 111: 8979
• 8c Norris DJ, Corrigan JF, Sun Y, Taylor NJ, Collins S. Can. J. Chem. 1993; 71: 1029
• 8d Trost BM, Shi Y. J. Am. Chem. Soc. 1991; 113: 701
• 8e Evans PA, Brandt TA. Tetrahedron Lett. 1996; 37: 1367
• 8f Bach RD, Klix RC. Tetrahedron Lett. 1986; 27: 1983
• 8g Kuroda C, Hirono H. Tetrahedron Lett. 1994; 35: 6895
• 9 Kotha S, Ali R, Tiwari A. Synlett 2013; 24: 1921
• 10 Swager TM. Synfacts 2013; 9: 1172
• 11a Fürstner A, Langemann K. J. Am. Chem. Soc. 1997; 119: 9130
• 11b Buschmann N, Ruckert NA, Blechert S. J. Org. Chem. 2002; 67: 4325
• 11c Davis FA, Yang BJ. J. Am. Chem. Soc. 2005; 127: 8398
• 12a Mori M, Sakakibara N, Kinoshita A. J. Org. Chem. 1998; 63: 6082
• 12b Kitamura T, Mori M. Org. Lett. 2001; 3: 1161
• 13a Kotha S, Khedkar P. Eur. J. Org. Chem. 2009; 730
• 13b Kotha S, Vittal S. Synlett 2011; 2329
• 13c Kotha S, Wagule GT. J. Org. Chem. 2012; 77: 6314
• 13d Comer E, Rohan E, Deng L, Porco JA. Org. Lett. 2007; 9: 2123
• 13e Zhou A, Rayabarapu D, Hanson PR. Org. Lett. 2009; 11: 531
• 13f Kotha S, Goyal D, Chavan AS. J. Org. Chem. 2013; 78: 12288
• 14a Okada T, Takeuchi D, Osakada K. Macromolecules 2010; 43: 9998
• 14b Ou J, Wong W.-T, Chiu P. Org. Biomol. Chem. 2012; 10: 5971
• 15 Duttagupta I, Goswami K, Sinha S. Tetrahedron 2012; 68: 8347
• 16 Jose MC, Juan LR, Andres AT. Tetrahedron Lett. 2004; 45: 1133
• 17a Kitamura M, Shintaku Y, Kudo D, Okauchi T. Tetrahedron Lett. 2010; 51: 4890
• 17b Konkol LC, Jones BT, Thomson RJ. Org. Lett. 2009; 11: 5550
• 18 Claraz A, Leroy J, Oudeyer S, Levacher V. J. Org. Chem. 2011; 76: 6457
• 19a Sylvester KT, Chirik PJ. J. Am. Chem. Soc. 2009; 131: 8772
• 19b Oh CH, Piao L, Kim JH. Synthesis 2013; 45: 174
• 20 Grotevendt GD, Lummiss JA. M, Mastronardi ML, Fogg DE. J. Am. Chem. Soc. 2011; 133: 15918
• 21 Kotha S, Manivannan E. J. Chem. Soc., Perkin Trans 1 2001; 2543
• 22 Paisdor B, Kuck D. J. Org. Chem. 1991; 56: 4753