The Awakening of a Sleeping Beauty: The ortho Photocycloaddition in the Total Synthesis of Protoilludane- and Prezizaene-Type ­Sesquiterpenes

Dedicated to Professor Masahiro Murakami.

Abstract

Photochemical cascade (domino) reactions provide a unique opportunity for the construction of complex molecular architectures. Specifically, an intramolecular ortho photocycloaddition of 7-(alkenyloxy)-indanones triggers a sequence of consecutive reactions that can lead in a single operation to the complete skeleton of two important classes of sesquiterpenes: protoilludanes and prezizaenes. In the former case, two transformations follow the initial photocycloaddition, while in the latter case, there are three consecutive transformations, two of which are initiated by a photon. Remarkably, the reaction cascades proceed with exquisite diastereoselectivity, generating three (protoilludane) or five (prezizaene) stereogenic centers with defined relative configurations.

1 Introduction

2 First Encounter and Initial Studies

3 Protoilludane-Type Sesquiterpenes

4 Prezizaene-Type Sesquiterpenes

5 Enantioselectivity

6 Perspective and Summary

Key words

cycloaddition - domino reaction - electrocyclic reactions - photochemistry - stereoselective synthesis - terpenoids

Publication History

Received: 20 May 2022

Accepted after revision: 07 July 2022

Article published online:
05 August 2022

• References and Notes


For comprehensive reviews on this topic, see:
• 1a Remy R, Bochet CG. Chem. Rev. 2016; 116: 9816
• 1b Hoffmann N. Photochem. Photobiol. Sci. 2012; 11: 1613
• 1c Streit U, Bochet CG. Beilstein J. Org. Chem. 2011; 7: 525
• 1d Streit U, Bochet CG. Chimia 2008; 62: 962
• 1e Hoffmann N. Synthesis 2004; 481
• 1f Cornelisse J., de Haan R.; ortho-Photocycloaddition of Alkenes and Alkynes to the Benzene Ring, In Molecular and Supramolecular Photochemistry, Vol. 8; Ramamurthy V, Schanze K, Dekker M. New York 2001: 1-126
• 1g Wagner PJ. Acc. Chem. Res. 2001; 34: 1
• 2a Angus HJ. F, Bryce-Smith D. Proc. Chem. Soc. 1959; 326
• 2b Schenck GO, Steinmetz R. Tetrahedron Lett. 1960; 1
• 2c Grovenstein Jr. E, Rao DV. Tetrahedron Lett. 1961; 148

Reviews:
• 3a Chappell D, Russell AT. Org. Biomol. Chem. 2006; 4: 4409
• 3b Cornelisse J. Chem. Rev. 1993; 93: 615
• 3c Wender PA, Siggel L, Nuss JM. Org. Photochem. 1989; 10: 357
• 4 For photochemical reactions, the given irradiation wavelength (λ) corresponds to the emission maximum of the irradiation source. When using glass filters, the wavelength is provided at which a relevant transmission (Pyrex λ: λ > 280 nm) is to be expected. For the unfiltered (quartz or Vycor λ glass) emission of mercury medium- and high-pressure lamps a wavelength of λ > 250 nm is given.
• 5a McCullough JJ, Huang CW. Can. J. Chem. 1969; 47: 757
• 5b Bowman RM, Calvo C, McCullough JJ, Miller RC, Singh I. Can. J. Chem. 1973; 51: 1060
• 6 Throughout this account, the relative configuration of racemates (denominated as rac-) is shown by straight bonds (bold or dashed), and the absolute and relative configurations of enantioenriched compounds by wedged bonds (bold or dashed), see: Maehr H. J. Chem. Educ 1985 62. 114
• 7 For a recent review, see: Okumura M, Sarlah D. Eur. J. Org. Chem 2020: 1259.

Examples include:
• 8a Wagner PJ, McMahon K. J. Am. Chem. Soc. 1994; 116: 10827
• 8b Nuss JM, Chinn JP, Murphy MM. J. Am. Chem. Soc. 1995; 117: 6801
• 8c Hoffmann N, Pete J.-P. J. Org. Chem. 1997; 62: 6952

For reviews covering the application of photochemical arene cycloaddition reactions to total syntheses, see:
• 9a Zhang Z, Zhou Y.-j, Liang X.-W. Org. Biomol. Chem. 2020; 18: 5558
• 9b Kärkäs MD, Porco JA. Jr, Stephenson CR. J. Chem. Rev. 2016; 116: 9683
• 9c Bach T, Hehn JP. Angew. Chem. Int. Ed. 2011; 50: 1000
• 9d Hoffmann N. Chem. Rev. 2008; 108: 1052
• 9e Iriondo-Alberdi J, Greaney MF. Eur. J. Org. Chem. 2007; 4801
• 10 Schneider F, Samarin K, Zanella S, Gaich T. Science 2020; 367: 676
• 11 Wagner PJ, Smart RP. Tetrahedron Lett. 1995; 36: 5135
• 12 Zech A, Bach T. J. Org. Chem. 2018; 83: 3069
• 13a Dilling WL, Tabor TE, Boer FP, North PP. J. Am. Chem. Soc. 1970; 92, 1399
• 13b Peet NP, Cargill RL, Bushey DF. J. Org. Chem. 1973; 38: 1218
• 13c Becker D, Nagler M, Hirsh S, Ramun J. J. Chem. Soc., Chem. Commun. 1983; 371
• 13d Becker D, Nagler M, Sahali Y, Haddad N. J. Org. Chem. 1991; 56: 4537
• 13e Kelly JF. D, Kelly JM, McMurry TB. H. J. Chem. Soc., Perkin Trans. 2 1999; 1933
• 13f Brimioulle R, Bauer A, Bach T. J. Am. Chem. Soc. 2015; 137: 5170
• 13g Graßl R, Jandl C, Bach T. J. Org. Chem. 2020; 85: 11426
• 14 Clericuzio M, Mella M, Toma L, Finzi PV, Vidari G. Eur. J. Org. Chem. 2002; 988
• 15 Zech A, Jandl C, Bach T. Angew. Chem. Int. Ed. 2019; 58: 14629
• 16a Wagner PJ, Nahm K. J. Am. Chem. Soc. 1987; 109: 4404
• 16b Wagner PJ, Nahm K. J. Am. Chem. Soc. 1987; 109: 6528
• 17 Crow WD, Engkaninan-Low U, Pang YT. Austr. J. Chem. 1984; 37: 1915
• 18 Connor DS, Klein GW, Taylor GN, Boeckman RK. Jr, Medwid JB. Org. Synth. 1972; 52: 16
• 19a Kabalka GW, Hutchins R, Natale NR, Yang DT. C, Broach V. Org. Synth. 1979; 59: 42
• 19b Shrestha ML, Qi W, McIntosh MC. J. Org. Chem. 2017; 82: 8359
• 20 Wuts PG. M. Greene’s Protective Groups in Organic Synthesis . 5th ed., Eds.; John Wiley & Sons; Hoboken: 2014: 385-388
• 21 Fujita K, Schlosser M. Helv. Chim. Acta 1982; 65: 1258
• 22 Hoffmann RW, Feussner G, Zeiss HJ, Schulz S. J. Organomet. Chem. 1980; 187: 321
• 23 Rodríguez Brasco MF, Seldes AM, Palermo JA. Org. Lett. 2001; 3: 1415
• 24 Nozoe S, Kobayashi H, Urano S, Furukawa J. Tetrahedron Lett. 1977; 18: 1381
• 25a Narzullaev AS, Yunusov MS, Yunusov SY. Chem. Nat. Compd. 1973; 9: 424
• 25b Tori M, Nakashima K, Seike M, Asakawa Y, Wright AD, König GM, Sticher O. Tetrahedron Lett. 1994; 35: 3105
• 26 Dess DB, Martin JC. J. Am. Chem. Soc. 1991; 113: 7277
• 27 Mogi Y, Inanaga K, Tokuyama H, Ihara M, Yamaoka Y, Yamada K.-i, Takasu K. Org. Lett. 2019; 21: 3954
• 28 Furukawa J, Morisaki N, Kobayashi H, Isawaki S, Nozoe S, Okuda S. Chem. Pharm. Bull. 1985; 33: 440
• 29 The rac-/ent-nomenclature is used throughout this account, as originally defined by Quinkert and Stark: Quinkert G, Stark H. Angew. Chem. Int. Ed. 1983; 22: 637

Reviews:
• 30a Banwell MG, Bon DJ.-Y. D. In Molecular Rearrangement in Organic Synthesis . Rojas CM. John Wiley & Sons; Hoboken: 2015: 261-288
• 30b Riguet E, Hoffmann N. In Comprehensive Organic Synthesis, 2nd ed., Vol. 5. Knochel P, Molander GA. Elsevier; Amsterdam: 2014: 200-221
• 30c Tsuno T. In Handbook of Synthetic Photochemistry . Albini A, Fagnoni M. Wiley-VCH; Weinheim: 2010: 95-135
• 30d Zimmerman HE, Armesto D. Chem. Rev. 1996; 96: 3065

Related examples:
• 31a van der Veen RH, Kruk C, Cerfontain H. J. Am. Chem. Soc. 1983; 105: 4367
• 31b Oren J, Schleifer L, Weinman S, Fuchs B. Chem. Commun. 1988; 315
• 31c Zimmerman HE, Chen W. Org. Lett. 2002; 4: 1155
• 31d Tröster A, Bauer A, Jandl C, Bach T. Angew. Chem. Int. Ed. 2019; 58: 3538
• 32 Næsborg L, Jandl C, Zech A, Bach T. Angew. Chem. Int. Ed. 2020; 59: 5656
• 33 Yang L, Yang Y.-L, Dong W.-H, Li W, Wang P, Cao X, Yuan J.-Z, Chen H.-Q, Mei W.-L, Dai H.-F. J. Enzyme Inhib. Med. Chem. 2019; 34: 853

For previous work on the synthesis of prezizaene-type sesquiterpenes, see:
• 34a Vettel PR, Coates RM. J. Org. Chem. 1980; 45: 5430
• 34b Piers E, Jean M, Marrs PS. Tetrahedron Lett. 1987; 28: 5075
• 34c Sakurai K, Kitahara T, Mori K. Tetrahedron 1990; 46: 761
• 34d Selvakumar N, Rao GS. R. S. J. Chem. Soc., Perkin Trans. 1 1994; 3217
• 34e Sharma MK, Banwell MG, Willis AC. Asian J. Org. Chem. 2014; 3: 632
• 35 Bruce D.-B, Sorrie AJ. S, Thomson RH. J. Chem. Soc. 1953; 2403
• 36 Rauscher N, Næsborg L, Jandl C, Bach T. Angew. Chem. Int. Ed. 2021; 60: 24039
• 37a Olah GA, Narang SC, Gupta BG. B, Malhotra R. J. Org. Chem. 1979; 44: 1247
• 37b Demuth M. In Modern Synthetic Methods, Vol. 4 1986; 102-104
• 38 Ziegler FE, Fang J. M, Tam CC. J. Am. Chem. Soc. 1982; 104: 7174
• 39 Barton DH. R, McCombie SW. J. Chem. Soc., Perkin Trans. 1 1975; 1574
• 40a Barton DH. R, Jang DO, Jaszberenyi JC. J. Org. Chem. 1993; 58: 6838
• 40b Shanker PS, Subba Rao GS. R. J. Chem. Soc., Perkin Trans. 1 1998; 539
• 41 Boto A, Hernández D, Hernández R, Suárez E. J. Org. Chem. 2006; 71: 1938
• 42a Corey EJ, Bakshi RK, Shibata S. J. Am. Chem. Soc. 1987; 109: 5551
• 42b Corey EJ, Helal J. Angew. Chem. Int. Ed. 1998; 37: 1986
• 43 Proessdorf J, Zech A, Jandl C, Bach T. Synlett 2020; 31: 1598
• 44 Prasad KR. K, Joshi NN. Tetrahedron: Asymmetry 1996; 7: 3147
• 45a Dale JA, Dull DL, Mosher HS. J. Org. Chem. 1969; 34: 2543
• 45b Dull DL, Mosher HS. J. Am. Chem. Soc. 1967; 89: 4230
• 45c Dale JA, Mosher HS. J. Am. Chem. Soc. 1973; 95: 512
• 45d Hoye T, Jeffrey CS, Shao F. Nat. Protoc. 2007; 2: 2451
• 46 Omura K, Swern D. Tetrahedron 1978; 34: 1651
• 47 Salmond WG, Barta MA, Havens JL. J. Org. Chem. 1978; 43: 2057
• 48a Coates RM, Ho Z, Klobus M, Wilson SR. J. Am. Chem. Soc. 1996; 118: 9249
• 48b Hong AY, Stoltz BM. Angew. Chem. Int. Ed. 2014; 53: 5248
• 48c Le Bideau F, Kousara M, Chen L, Wei L, Dumas F. Chem. Rev. 2017; 117: 6110
• 48d Radulović NS, Mladenović MZ, Stojanović NM, Blagojević PD. J. Nat. Prod. 2019; 82: 1874
• 49 Rauscher N., Bach T. unpublished results.

Recent reviews:
• 50a Großkopf J, Kratz T, Rigotti T, Bach T. Chem. Rev. 2022; 122: 1626
• 50b Schwinger DP, Bach T. Acc. Chem. Res. 2020; 53: 1933

Recent work:
• 51a Li X, Großkopf J, Jandl C, Bach T. Angew. Chem. Int. Ed. 2021; 60: 2684
• 51b Pecho F, Sempere Y, Gramüller J, Hörmann FM, Gschwind RM, Bach T. J. Am. Chem. Soc. 2021; 143: 9350
• 51c Plaza M, Großkopf J, Breitenlechner S, Bannwarth C, Bach T. J. Am. Chem. Soc. 2021; 143: 11209
• 51d Großkopf J, Plaza M, Seitz A, Breitenlechner S, Storch G, Bach T. J. Am. Chem. Soc. 2021; 143: 21241
• 52 Stegbauer S, Jandl C, Bach T. Angew. Chem. Int. Ed. 2018; 57: 14593
• 53 For a recent review on the synthesis of various polycyclic terpenes, see: Chesnokov GA, Gademann K. Chem. Commun. 2022; 58: 4941