Stereoselective access to [5.5.0] and [4.4.1] bicyclic compounds through Pd-catalysed divergent higher-order cycloadditions.
Journal
Nature chemistry
ISSN: 1755-4349
Titre abrégé: Nat Chem
Pays: England
ID NLM: 101499734
Informations de publication
Date de publication:
09 2020
09 2020
Historique:
received:
09
07
2019
accepted:
01
06
2020
pubmed:
29
7
2020
medline:
29
7
2020
entrez:
29
7
2020
Statut:
ppublish
Résumé
Medium-sized rings, including those embedded in bridged and fused bicyclic scaffolds, are common core structures of myriad bioactive molecules. Among various synthetic strategies towards their synthesis, intermolecular higher-order cycloaddition provides great potential to build complex medium-sized rings from simple building blocks. Unfortunately, such transformations are often plagued with competitive reaction pathways and low levels of site- and stereoselectivity. Herein, we report catalyst-controlled divergent access to three classes of medium-sized bicyclic compounds in high efficiency and stereoselectivity, by palladium-catalysed cycloadditions of tropones with γ-methylidene-δ-valerolactones. Mechanistic studies and density functional theory calculations disclosed that the divergent reactions stem from the different reaction profiles of the diastereomeric intermediates. While one undergoes either O- or C-allylation to provide [5.5.0] or [4.4.1] bicyclic compounds, the unique conformation of the other diastereomer allows an unconventional alkene isomerization to deliver bridgehead alkene-containing bicyclo[4.4.1] compounds. The conversion of these products to diverse complex polycyclic scaffolds has also been demonstrated.
Identifiants
pubmed: 32719481
doi: 10.1038/s41557-020-0503-7
pii: 10.1038/s41557-020-0503-7
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
860-868Références
Devon, T. K. Handbook of Naturally Occurring Compounds Vol. 1 (Elsevier, 2012).
Takasaki, M. et al. Inhibitors of skin-tumor promotion. VIII. Inhibitory effects of euglobals and their related compounds on Epstein–Barr virus activation. Chem. Pharm. Bull. 38, 2737–2739 (1990).
Tran, D. N. & Cramer, N. Biomimetic synthesis of (+)-ledene, (+)-viridiflorol, (−)-palustrol, (+)-spathulenol, and psiguadial A, C, and D via the platform terpene (+)-bicyclogermacrene. Chem. Eur. J. 20, 10654–10660 (2014).
pubmed: 24867775
Kuwajima, I. & Tanino, K. Total synthesis of ingenol. Chem. Rev. 105, 4661–4670 (2005).
pubmed: 16351057
Jørgensen, L. et al. 14-Step synthesis of (+)-ingenol from (+)-3-carene. Science 341, 878–882 (2013).
pubmed: 23907534
Amagata, T. et al. Unusual C25 steroids produced by a sponge-derived Penicillium citrinum. Org. Lett. 5, 4393–4396 (2003).
pubmed: 14602008
Liu, J. et al. Asymmetric total synthesis of cyclocitrinol. J. Am. Chem. Soc. 140, 5365–5369 (2018).
pubmed: 29617567
Anslyn, E. V. & Dougherty, D. A. Modern Physical Organic Chemistry (University Science Books, 2006).
Yet, L. Metal-mediated synthesis of medium-sized rings. Chem. Rev. 100, 2963–3008 (2000).
pubmed: 11749312
Rigby, J. H. Transition metal promoted higher-order cycloaddition reactions in organic synthesis. Acc. Chem. Res. 26, 579–585 (1993).
Palazzo, T. A., Mose, R. & Jørgensen, K. A. Cycloaddition reactions: why is it so challenging to move from six to ten electrons? Angew. Chem. Int. Ed. 56, 10033–10038 (2017).
Palazzo, T. A. & Jørgensen, K. A. Higher-order cycloaddition reactions: a computational perspective. Tetrahedron 74, 7381–7387 (2018).
Trost, B. M., McDougall, P. J., Hartmann, O. & Wathen, P. T. Asymmetric synthesis of bicyclo[4.3.1]decadienes and bicyclo[3.3.2]decadienes via [6+3] trimethylenemethane cycloaddition with tropones. J. Am. Chem. Soc. 130, 14960–14961 (2008).
pubmed: 18937462
pmcid: 2665030
Trost, B. M. & McDougall, P. J. Access to a welwitindolinone core using sequential cycloadditions. Org. Lett. 11, 3782–3785 (2009).
pubmed: 19606876
pmcid: 2736368
Liu, H. et al. Metal-catalyzed [6+3] cycloaddition of tropone with azomethine ylides: a practical access to piperidine-fused bicyclic heterocycles. J. Am. Chem. Soc. 136, 2625–2629 (2014).
pubmed: 24450417
Teng, H. –L., Yao, L. & Wang, C. –J. Cu(I)-catalyzed regio- and stereoselective [6+3] cycloaddition of azomethine ylides with tropone: an efficient asymmetric access to bridged azabicyclo[4.3.1]decadienes. J. Am. Chem. Soc. 136, 4075–4080 (2014).
pubmed: 24564408
Xie, M. et al. Catalytic asymmetric [8+2] cycloaddition: synthesis of cycloheptatriene-fused pyrrole derivatives. Angew. Chem. Int. Ed. 52, 5604–5607 (2013).
Wang, S., Rodríguez-Escrich, C. & Pericàs, M. A. Catalytic asymmetric [8+2] annulation reactions promoted by a recyclable immobilized isothiourea. Angew. Chem. Int. Ed. 56, 15068–15072 (2017).
Mose, R. et al. Organocatalytic stereoselective [8+2] and [6+4] cycloadditions. Nat. Chem. 9, 487–492 (2017).
pubmed: 28430196
Tejero, R., Ponce, A., Adrio, J. & Carretero, J. C. Ni-catalyzed [8+3] cycloaddition of tropones with 1, 1-cyclopropanediesters. Chem. Commun. 49, 10406–10408 (2013).
Zhang, J. et al. Catalytic asymmetric [8+3] annulation reactions of tropones or azaheptafulvenes with meso-aziridines. Chem. Eur. J. 24, 13428–13431 (2018).
pubmed: 29992640
Yu, P. et al. Organocatalytic [6+4] cycloadditions via zwitterionic intermediates: chemo-, regio-, and stereoselectivities. J. Am. Chem. Soc. 140, 13726–13735 (2018).
pubmed: 30251535
Inagaki, F., Sugikubo, K., Miyashita, Y. & Mukai, C. Rhodium(I)-catalyzed intramolecular [5+2] cycloaddition reactions of alkynes and allenylcyclopropanes: construction of bicyclo[5.4.0]undecatrienes and bicyclo[5.5.0]dodecatrienes. Angew. Chem. Int. Ed. 49, 2206–2210 (2010).
Mei, G., Liu, X., Qiao, C., Chen, W. & Li, C.-C. Type II intramolecular [5+2] cycloaddition: facile synthesis of highly functionalized bridged ring systems. Angew. Chem. Int. Ed. 54, 1754–1758 (2015).
Liu, X. et al. Recent synthetic studies towards natural products via [5+2] cycloaddition reactions. Org. Chem. Front. 5, 1217–1228 (2018).
Wang, M., Rong, Z. –Q. & Zhao, Y. Stereoselective synthesis of epsilon-lactones or spiro-heterocycles through NHC-catalyzed annulation: divergent reactivity by catalyst control. Chem. Commun. 50, 15309–15312 (2014).
Yang, L. –C. et al. Construction of nine-membered heterocycles through palladium-catalyzed formal [5+4] cycloaddition. Angew. Chem. Int. Ed. 56, 2927–2931 (2017).
Rong, Z. –Q. et al. Nine-membered benzofuran-fused heterocycles: enantioselective synthesis by Pd-catalysis and rearrangement via transannular bond formation. J. Am. Chem. Soc. 139, 15304–15307 (2017).
pubmed: 29039659
Wang, Y. –N. et al. Pd-catalyzed enantioselective [6+4] cycloaddition of vinyl oxetanes with azadienes to access ten-membered heterocycles. Angew. Chem. Int. Ed. 57, 1596–1600 (2018).
Takeshita, H., Wada, Y., Mori, A. & Hatsui, T. The cycloaddition reaction of isobenzofuran with some tropones. Chem. Lett. 2, 335–336 (1973).
Li, P. & Yamamoto, H. Lewis acid catalyzed inverse-electron-demand Diels–Alder reaction of tropones. J. Am. Chem. Soc. 131, 16628–16629 (2009).
pubmed: 19886665
pmcid: 2810398
Hammer, N. et al. Catalytic asymmetric [4+2]-cycloadditions using tropolones: developments, scope, transformations, and bioactivity. Angew. Chem. Int. Ed. 57, 13216–13220 (2018).
Shintani, R., Murakami, M. & Hayashi, T. γ-Methylidene-δ-valerolactones as a coupling partner for cycloaddition: palladium-catalyzed [4+3] cycloaddition with nitrones. J. Am. Chem. Soc. 129, 12356–12357 (2007).
pubmed: 17894493
Shintani, R., Park, S., Shirozu, F., Murakami, M. & Hayashi, T. Palladium-catalyzed asymmetric decarboxylative lactamization of γ-methylidene-δ-valerolactones with isocyanates: conversion of racemic lactones to enantioenriched lactams. J. Am. Chem. Soc. 130, 16174–16175 (2008).
pubmed: 18998676
Shintani, R., Tsuji, T., Park, S. & Hayashi, T. Mechanistic investigation of the palladium-catalyzed decarboxylative cyclization of γ-methylidene-δ-valerolactones with isocyanates: kinetic studies and origin of the site selectivity in the nucleophilic attack at a (π-allyl)palladium. J. Am. Chem. Soc. 132, 7508–7513 (2010).
pubmed: 20450179
Trost, B. M. & Seoane, P. R. [6+3] Cycloaddition to nine-membered ring carbocycles. J. Am. Chem. Soc. 109, 615–617 (1987).
Wu, S., Mori, A. & Takeshita, H. Formations of an [8π + 4π] cycloadduct via an electron-transfer mechanism and a meta-cycloadduct by irradiations of tropone and 9,10-dicyanoanthracene. J. Chem. Soc. Chem. Commun. 1994, 919–920 (1994).
Zhao, Y. & Truhlar, D. G. Density functionals with broad applicability in chemistry. Acc. Chem. Res. 41, 157–167 (2007).
Zhao, Y. & Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 120, 215–241 (2008).
Haibach, M. C. & Seidel, D. C–H bond functionalization through intramolecular hydride transfer. Angew. Chem. Int. Ed. 53, 5010–5036 (2014).
Wang, L. & Xiao, J. Hydrogen-atom transfer reactions. Top. Curr. Chem. 374, 17 (2016).
Kumar, P., Thakur, A., Hong, X., Houk, K. N. & Louie, J. Ni(NHC)]-catalyzed cycloaddition of diynes and tropone: apparent enone cycloaddition involving an 8π insertion. J. Am. Chem. Soc. 136, 17844–17851 (2014).
pubmed: 25416006
pmcid: 4291811
Trost, B. M. & Van Vranken, D. L. Asymmetric transition metal-catalyzed allylic alkylations. Chem. Rev. 96, 395–422 (1996).
pubmed: 11848758
Trost, B. M. & Schultz, J. E. Palladium-catalyzed asymmetric allylic alkylation strategies for the synthesis of acyclic tetrasubstituted stereocenters. Synthesis 51, 1–30 (2019).
Mark, J. Y. W., Pouwer, R. H. & Williams, C. M. Natural products with anti-Bredt and bridgehead double bonds. Angew. Chem. Int. Ed. 53, 13664–13688 (2014).