Synthesis of Functionalized Cyclopentene Derivatives through Gold-Catalyzed Reaction of Stabilized Vinyldiazo Compounds and Styrenes

Abstract

The reaction of alkenyldiazo compounds with styrene derivatives in the presence of [Au(IPr)(MeCN)][SbF₆] provided cyclopentene derivatives resulting from a formal [3+2] cycloaddition reaction as major products. This reaction outcome stands in marked contrast to that previously observed for other olefinic derivatives. From a mechanistic point of view, this process would involve the initial generation of a highly electrophilic alkenylgold carbene intermediate, which would be subsequently involved in a stepwise carbocationic process.

Key words

gold - cyclopentenes - diazo compounds - styrene derivatives - [3+2] carbocycloaddition

• References


For selected recent reviews on gold catalysis, see:
• 1a Huple DB. Ghorpade S. Liu R.-S. Adv. Synth. Catal. 2016; 358: 1348
• 1b Dorel R. Echavarren AM. Chem. Rev. 2015; 115: 9028
• 1c Fürstner A. Acc. Chem. Res. 2014; 47: 925
• 1d Obradors C. Echavarren AM. Acc. Chem. Res. 2014; 47: 902
• 1e Fensterbank L. Malacria M. Acc. Chem. Res. 2014; 47: 953
• 1f Rudolph M. Hashmi AS. K. Chem. Soc. Rev. 2012; 41: 2448
• 1g Krause N. Winter C. Chem. Rev. 2011; 111: 1994
• 1h Aubert C. Fensterbank L. Garcia P. Malacria M. Simonneau A. Chem. Rev. 2011; 111: 194
• 1i Fürstner A. Chem. Soc. Rev. 2009; 38: 3208
• 1j Hashmi AS. K. Rudolph M. Chem. Soc. Rev. 2008; 37: 1766
• 1k Jiménez-Núñez E. Echavarren AM. Chem. Rev. 2008; 108: 3326
• 1l Gorin GJ. Sherry BD. Toste FD. Chem. Rev. 2008; 108: 3351
• 1m Hashmi AS. K. Chem. Rev. 2007; 107: 3180

For recent reviews on the reaction mechanisms of gold-catalyzed transformations of unsaturated substrates, see:
• 2a Yang W. Hashmi AS. K. Chem. Soc. Rev. 2014; 43: 2941
• 2b Obradors C. Echavarren AM. Chem. Commun. 2014; 16
• 3 For a seminal contribution on gold-catalyzed transformations of ethyl diazoacetate, see: Fructos MR. Belderrain TR. de Frémont P. Scott NM. Nolan SP. Díaz-Requejo MM. Pérez PJ. Angew. Chem. Int. Ed. 2005; 44: 5284

For recent reviews on the gold chemistry of diazo compounds, see:
• 4a Fructos MR. Díaz-Requejo MM. Pérez PJ. Chem. Commun. 2016; 7326
• 4b Wei F. Song C. Ma Y. Zhou L. Tung C.-H. Xu Z. Sci. Bull. 2015; 60: 1479
• 4c Liu L. Zhang J. Chem. Soc. Rev. 2016; 45: 506
• 5 For a seminal contribution on gold-catalyzed transformations of stabilized vinyldiazo derivatives, see: Pagar VV. Jadhav AM. Liu R.-S. J. Am. Chem. Soc. 2011; 133: 20728

For selected gold-catalyzed reactions of stabilized vinyldiazo compounds involving alkenylgold carbene intermediates, see:
• 6a Xu G. Zhu C. Gu W. Li J. Sun J. Angew. Chem. Int. Ed. 2015; 54: 883
• 6b Zhang D. Xu G. Ding D. Zhu C. Li J. Sun J. Angew. Chem. Int. Ed. 2014; 53: 11070
• 6c López E. Lonzi G. López LA. Organometallics 2014; 33: 5924
• 6d Lonzi G. López LA. Adv. Synth. Catal. 2013; 355: 1948
• 7 Barluenga J. Lonzi G. Tomás M. López LA. Chem. Eur. J. 2013; 19: 1573

For representative examples of rhodium(II)-catalyzed decomposition of vinyldiazomethanes in the presence of styrenes leading to cyclopropane derivatives, see:
• 8a Davies HM. L. Bruzinski PR. Lake DH. Kong N. Fall MJ. J. Am. Chem. Soc. 1996; 118: 6897
• 8b Qin C. Boyarskikh V. Hansen JH. Hardcastle KI. Musaev DG. Davies HM. L. J. Am. Chem. Soc. 2011; 133: 19198
• 8c An alternative reaction course (combined C–H functionalization/Cope rearrangement) has been also reported for some cyclic alkenes as well as allyl and vinyl ethers, see: Davies HM. L. Lian Y. Acc. Chem. Res. 2012; 45: 923

For selected cyclopropanation reactions of alkenylgold carbenoids generated from cyclopropenes and propargylic esters, see:
• 9a Miege F. Meyer C. Cossy J. Chem. Eur. J. 2012; 18: 7810
• 9b Miege F. Meyer C. Cossy J. Org. Lett. 2010; 12: 4144
• 9c Bauer JT. Hadfield MS. Lee A.-L. Chem. Commun. 2008; 6405
• 9d Shapiro ND. Toste FD. J. Am. Chem. Soc. 2008; 130: 9244
• 9e Gorin DJ. Dubé P. Toste FD. J. Am. Chem. Soc. 2006; 128: 14480
• 9f Johansson MJ. Gorin DJ. Staben ST. Toste FD. J. Am. Chem. Soc. 2005; 127: 18002
• 10 For a recent review covering coinage metal catalyzed transformations of stabilized vinyldiazo compounds developed in our research group and others, see: López E. González-Pelayo S. López LA. Chem. Rec. 2017; 17: 312
• 11a For gold-catalyzed [3+2] carbocyclization reactions of stabilized vinyldiazo derivatives and enolethers, see: Briones JF. Davies HM. L. J. Am. Chem. Soc. 2013; 135: 13314

For gold-catalyzed [3+2] carbocyclization reactions of stabilized vinyldiazo compounds and allene derivatives, see:
• 11b López E. González J. López LA. Adv. Synth. Catal. 2016; 358: 1428
• 11c López E. Lonzi G. González J. López LA. Chem. Commun. 2016; 9398
• 12 Kabalka GW. Dong G. Venkataiah B. Chen C. J. Org. Chem. 2005; 70: 9207
• 13 Regarding the formation of cyclopentene derivative 5 in the reaction of methoxy-4-vinylbenzene (2e), we argue that the half-life of the intermediate II is enhanced by the strong donor methoxy group, thus allowing species II to undergo another regioselective alkene insertion with generation of a new carbocationic intermediate. Final cyclization reaction would afford cycloheptene derivative 5.
• 14 This reactivity pattern had been previously observed in the gold-catalyzed reactions of stabilized vinyldiazo compounds and several electron-rich arenes, see reference 7.
• 15 The effect of the substitution on the regiochemical outcome (carbenoid versus vinylogous reactivity) had been previously reported for rhodium(II)-stabilized vinylcarbenoids. In particular, it was found that vinyldiazo compounds containing a substituent at the vinyl terminus exhibited normal carbenoid reactivity affording the cyclopropanation products in good yields, see: Davies HM. L. Hu B. Saikali E. Bruzinski PR. J. Org. Chem. 1994; 59: 4535
• 16a Padwa A. Kulkarni YS. Zhang Z. J. Org. Chem. 1990; 55: 4144
• 16b Davies HM. L. Hougland PW. Cantrell JrW. R. Synth. Commun. 1992; 22: 971
• 16c Doyle MP. Yan M. Hu W. Gronenberg L. J. Am. Chem. Soc. 2003; 125: 4692
• 16d Peng C. Cheng J. Wang J. J. Am. Chem. Soc. 2007; 129: 8708
• 17 Davies HM. L. Panaro SA. Tetrahedron 2008; 56: 4871