The Trajectory of the (η5-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

Jonathan J. Wong; Xiangyang Chen; Kendall N. Houk; K. Peter C. Vollhardt

doi:10.1055/a-1645-2632

Synthesis, Table of Contents

Synthesis 2021; 53(22): 4279-4289
DOI: 10.1055/a-1645-2632

special topic

Special Issue dedicated to Prof. Sarah Reisman, recipient of the 2019 Dr. Margaret Faul Women in Chemistry Award

The Trajectory of the (η ⁵-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

Jonathan J. Wong

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

Xiangyang Chen

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

Kendall N. Houk ∗

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

K. Peter C. Vollhardt ∗

^bDepartment of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA

› Author Affiliations

Abstract

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Congratulations to Professor Sarah Reisman at the California Institute of Technology for having been chosen as the first recipient of the Dr. Margaret Faul Award for Women in Chemistry

Abstract

The mechanisms by which the complexes CpCoL₂ (Cp = C₅H₅; L = CO or CH₂=CH₂) mediate the cycloisomerizations of α,δ,ω-enynenes containing allylic ether linkages are probed by DFT methods. The outcomes corroborate experimental results and provide energetic and structural details of the trajectories leading to 3-(oxacyclopentyl or cycloalkyl)furans via the intermediacy of isolable CpCo-η ⁴-dienes. They comprise initial stereoselective complexation of one of the double bonds and the triple bond, rate-determining oxidative coupling to a triplet 16e cobalta-2-cyclopentene, and terminal double bond docking, followed by stereocontrolled insertion to assemble intermediate cis- and trans-fused triplet cobalta-4-cycloheptenes. A common indicator of the energetic facility of the latter is the extent of parallel alignment of the alkene moiety and its target Co–Cα bond. The cobalta-4-cycloheptenes transform further by β-hydride elimination–reductive elimination to furnish CpCo-η ⁴-dienes, which are sufficiently kinetically protected to allow for their experimental observation. The cascade continues through cobalt-mediated hydride shifts and dissociation of the aromatic furan ring. The findings in silico with respect to the stereo-, regio-, and chemoselectivity are in consonance with those obtained in vitro.

Key words

DFT - enynes - β-hydride elimination - cobalt - cycloisomerization - furans

Full Text

References

References
1 Chang C.-A, Gürtzgen S, Johnson EP, Vollhardt KP. C. Synthesis 2020; 52: 399

For some recent reviews of related isomerizations, see:

2a Liu X, Li B, Liu Q. Synthesis 2019; 51: 1293
2b Ai W, Zhong R, Liu X, Liu Q. Chem. Rev. 2019; 119: 2876
2c Hirano M. ACS Catal. 2019; 9: 1408
2d Pellissier H. Coord. Chem. Rev. 2018; 360: 122
2e Hu Y, Bai M, Yang Y, Zhou Q. Org. Chem. Front. 2017; 4: 2256
2f Chen W.-W, Xu M.-H. Org. Biomol. Chem. 2017; 15: 1029
2g Röse P, Hilt G. Synthesis 2016; 48: 463
2h Stathakis CI, Gkizis PL, Zografos AL. Nat. Prod. Rep. 2016; 33: 1093
2i Gandeepan P, Cheng C.-H. Acc. Chem. Res. 2015; 48: 1194
2j Micalizio GC, Hale SB. Acc. Chem. Res. 2015; 48: 663

For a topical review, see:

3a Domínguez G, Pérez-Castells J. Chem. Eur. J. 2016; 22: 6720

For examples of pertinent intramolecular dienyne cycloisomerizations, see ref. 1 and:

3b Suleymanov AA, Vasilyev DV, Novikov VV, Nelyubina YV, Perekalin DS. Beilstein J. Org. Chem. 2017; 13: 639 ; and references cited therein
3c Lanzi M, Santacroce V, Balestri D, Marchiò L, Bigi F, Maggi R, Malacria M, Maestri G. Angew. Chem. Int. Ed. 2019; 58: 6703 ; and references cited therein

For an excellent review, see:

4a Roglans A, Pla-Quintana A, Solà M. Chem. Rev. 2021; 121: 1894

For a collection of specific examples, see:

4b Delorme M, Punter A, Oliveira R, Aubert C, Carissan Y, Parrain J.-L, Amatore M, Nava P, Commeiras L. Dalton Trans. 2019; 48: 15767
4c Anderson EA, Paton RS. Chimia 2018; 72: 614
4d Cassú D, Parella T, Solà M, Pla-Quintana A, Roglans A. Chem. Eur. J. 2017; 23: 14889
4e Kiyota S, In S, Komine N, Hirano M. Chem. Lett. 2017; 46: 1040
4f Yang T, Ehara M. J. Org. Chem. 2017; 82: 2150
4g Mekareeya A, Walker PR, Couce-Rios A, Campbell CD, Steven A, Paton R, Anderson EA. J. Am. Chem. Soc. 2017; 139: 10104
4h Hirano M, Ueda T, Komine N, Komiya S, Nakamura S, Deguchi H, Kawauchi S. J. Organomet. Chem. 2015; 797: 174
4i Haraburda E, Torres O, Parella T, Solà M, Pla-Quintana A. Chem. Eur. J. 2014; 20: 5034
4j Liu T, Han L, Han S, Bi S. Organometallics 2014; 34: 280
4k Hong X, Liu P, Houk KN. J. Am. Chem. Soc. 2013; 135: 1456
4l Dachs A, Pla-Quintana A, Parella T, Solà M, Roglans A. Chem. Eur. J. 2011; 17: 14493
4m Varela JA, Saá C. J. Organomet. Chem. 2009; 694: 143
4n Clavier H, Correa A, Escudero-Adán EC, Benet-Buchholz J, Cavallo L, Nolan SP. Chem. Eur. J. 2009; 15: 10244
4o Montero-Campillo MM, Rodríguez-Otero J, Cabaleiro-Lago E. J. Phys. Chem. A 2008; 112: 2423

For our DFT appraisals with pertinent CpCo systems, see:

5a Lebœuf D, Iannazzo L, Geny A, Malacria M, Vollhardt KP. C, Aubert C, Gandon V. Chem. Eur. J. 2010; 16: 8904
5b Aubert C, Gandon V, Geny A, Heckrodt TJ, Malacria M, Paredes E, Vollhardt KP. C. Chem. Eur. J. 2007; 13: 7466
5c Geny A, Lebœuf D, Rouquié G, Vollhardt KP. C, Malacria M, Gandon V, Aubert C. Chem. Eur. J. 2007; 13: 5408
5d Agenet N, Gandon V, Vollhardt KP. C, Malacria M, Aubert C. J. Am. Chem. Soc. 2007; 129: 8860
5e Gandon V, Agenet N, Vollhardt KP. C, Malacria M, Aubert C. J. Am. Chem. Soc. 2006; 128: 8509

6 Hong P, Yamamoto Y, Yamazaki H. J. Organomet. Chem. 1982; 232: 71
7 For a review, see: Espinet P, Albéniz AC. Fundamentals of Molecular Catalysis . Kurosawa H, Yamamoto A. Elsevier; Amsterdam: 2003: 293

The cycloheptene frame is conformationally very flexible, see:

8a Leong MK, Mastryukov VS, Boggs JE. J. Mol. Struct. 1998; 445: 149
8b Borgen G. Acta Chem. Scand., Ser. B 1974; 28: 135
8c St Jacques M, Vaziri C. Can J. Chem. 1971; 49: 1256
8d Neto N, Di Lauro C, Califano S. Spectrochim. Acta, Part A 1970; 26: 1489
8e For the first postulation of such a cobaltacycloheptene ring flip, see: Wakatsuki Y, Aoki K, Yamazaki H. J. Am. Chem. Soc. 1979; 101: 1123
8f See also: Scozzafava M, Stolzenberg AM. Organometallics 1988; 7: 1073

9a Cammack JK, Jalisatgi S, Matzger AJ, Negrón A, Vollhardt KP. C. J. Org. Chem. 1996; 61: 4798
9b King JA. Jr, Vollhardt KP. C. J. Organomet. Chem. 1993; 460: 91

10 For a tabulation of van der Waals radii, see: Alvarez S. Dalton Trans. 2013; 42: 8617

For selected pertinent discussions of steric and electronic effects on β-hydride eliminations, see:

11a Chen Z.-M, Liu J, Guo J.-Y, Loch M, DeLuca RJ, Sigman MS. Chem. Sci. 2019; 10: 7246 ; and references cited therein
11b Giri R, Shekhar KC. J. Org. Chem. 2018; 83: 3013
11c Jana R, Pathak TP, Sigman MS. Chem. Rev. 2011; 111: 1417
11d Gómez-Gallego M, Sierra MA. Chem. Rev. 2011; 111: 4857
11e Piers WE, Collins S. In Comprehensive Organometallic Chemistry III, Vol. 1. Mingos DM. P, Crabtree RH. Elsevier; Amsterdam: 2007: 141
11f Lu X. Top. Catal. 2005; 35: 73
11g Sen A, Kang M. In Late Transition Metal Polymerization Catalysis . Rieger B, Saunders Baugh L, Kacker S, Striegler S. Wiley-VCH; Weinheim: 2003: 307
11h Trost BM, Romero DL, Rise F. J. Am. Chem. Soc. 1994; 116: 4268
11i Trost BM, Tanoury GJ, Lautens M, Chan C, MacPherson DT. J. Am. Chem. Soc. 1994; 116: 4255
11j Trost BM, Lautens M, Chan C, Jebaratnam DJ, Mueller T. J. Am. Chem. Soc. 1991; 113: 636
11k Trost BM, Lee DC, Rise F. Tetrahedron Lett. 1989; 30: 651

12a For a seminal report, see: Doherty, N. M.; Bercaw, J. E. J. Am. Chem. Soc. 1985, 107, 2670; and citing references
12b For a recent treatment, see: Wheeler JI, Carlsen R, Ess DH. Dalton Trans. 2020; 49: 7747

Supplementary Material

The Trajectory of the (η 5-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

The Trajectory of the (η ⁵-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal