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A Palladium/Norbornene Cooperative Catalysis to Access Tetrahdronaphthalenes and Indanes with a Quaternary Center Zeshui Liu, Guangyin Qian, Qianwen Gao, Peng Wang, Hong-Gang Cheng, Qiang Wei, Qi Liu, and Qianghui Zhou ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b00975 • Publication Date (Web): 20 Apr 2018 Downloaded from http://pubs.acs.org on April 20, 2018
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ACS Catalysis
Ze-Shui Liu‡1, Guangyin Qian‡1, Qianwen Gao1, Peng Wang1, Hong-Gang Cheng1, Qiang Wei1, Qi Liu1 and Qianghui Zhou*,1,2 1 2
College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, China The Institute for Advanced Studies, Wuhan University, 430072, Wuhan, China
ABSTRACT: A cooperative catalytic system comprising a palladium/XPhos complex and 5-norbornene-2-carboxylic acid was developed. This system promotes a two-component annulation reaction, allowing the construction of tetrahydronaphthalenes and indanes that contain quaternary centers through consecutive Catellani-type C-H activation and redox-relay Heck reaction. Inexpensive 5-norbornene-2-carboxylic acid acts as a catalytic mediator (20 mol%) in this process. This mild, scalable and chemo-selective protocol is compatible with a wide variety of readily available aryl iodides and alkylating reagents. Application of this method in a 4step synthesis of opioid analgesic eptazocine is demonstrated. Preliminary studies underscore the future promise of rendering this Catellani/redox-relay Heck cascade enantioselective. KEYWORDS: Catellani reaction, redox-relay Heck, indane, tetrahydronaphthalene, quaternary center
Tetrahydronaphthalenes or indanes, particularly those containing benzylic quaternary centers, are prevalent motifs in bioactive natural products1-4 and therapeutic agents5,6 (e.g., (+)-
Figure 1. Approaches to access tetrahydronaphthalene or indane scaffold with a quaternary center.
halenaquinone,1 furanosteroid viridin,2 cannabispirenone A,3 haouamine A,4 and opioid analgesics (‒)-eptazocine5 and (‒)etazocine6 etc) (Figure 1A). As such, efficient means to access these priviledged scaffolds are highly desirable. Typically, tetrahydronaphthalenes and indanes can be synthesized through intramolecular Friedel-Crafts type alkylation of the corresponding benzenes,7 transition metal catalyzed cycloadditions8 or cycloisomerizations,9 intramolecular Heck reactions,10 or radical mediated cyclizations,11 etc (Figure 1B). However, these methods generally require specially functionalized precursors, significantly limiting their scopes. Moreover, strategies for effective establishment of the required benzylic quaternary center are very limited.10a-b,12-14 Hence, a general approach that can efficiently synthesize the benzo-fused rings with a benzylic quaternary center from readily available building blocks remains to be realized . The Catellani reaction has recently emerged as a powerful method that permits the expeditious syntheses of highly substituted arenes.15 It utilizes cooperative palladium and 2norbornene (NBE) catalysis to facilitate sequential ortho C–H functionalization and ipso coupling of aryl iodide, thereby allowing the simultaneous functionalization of ortho and ipso positions.16 Notably, Lautens,17 Catellani18 and others19 have developed a gamut of elegant Catellani-type annulation methods for the syntheses of various benzo-fused rings. Inspired by the innovative research from the Sigman group,20 we envisaged that a novel Catellani/redox-relay Heck cascade21 as depicted in Figure 1C could offer a convergent synthetic route to the aforementioned complex scaffolds or analogs thereof. We surmised that the aryl iodide 1 and olefinic alcohol containing alkylating reagent 2 would engage in sequential intermolecular Catellani reaction (intermediate A to D) and intramolecular redox-relay Heck cyclization (intermediate D to product 3 via intermediate E).20c Such a sequence would enable the formation of two C-C bonds, the creation of a benzylic quaternary center, and the installation of
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a diversifiable carbonyl functionality in a single operation.22 Hence, the proposed Catellani/redox-relay Heck cascade will offer a novel and convergent route to the aforementioned target molecules from readily available starting materials.
Preliminary studies commenced with a model reaction involving readily available 1-iodonaphthalene (1a) and (E)-6bromo-3-methylhex-2-en-1-ol (2a)23 as the reactants (Table 1). [Pd(C3H5)Cl]2 was initially chosen as the catalyst (10 mol%), with PPh3 serving as the ligand (22 mol%), K2CO3 as the base (3.0 equiv), and MeCN as the solvent. The reaction employing 50 mol% norbornene (N1) as the mediator furnished the desired product 3aa in 37% yield (Entry 1). In an attempt to improve the overall efficiency, various norbornene derivatives were then examined, including the Dong24 and Yu25 mediators (Entries 2 and 3), which did not improve the efficiency of this process. Gratifyingly, the inexpensive NBE derivative, 5-norbornene-2carboxylic acid N4 was identified as the optimal mediator (Entry 4),26 affording 3aa in a substantially improved yield (91%), whereas only trace product was obtained with norbornene diacid derivative N5 serving as the mediator (Entry 5). Further optimization indicated that the amount of the mediator N4 can be reduced without deleterious effects on the yield. For instance, the use of 20 mol% of N4 provided 3aa in 77% yield (Entry 6). Additional studies focused on modifications to the phosphine ligands, which was found to play a critical role in this process. When the bidentate ligand DPPE (Entry 9) or BIANP (Entry 10) were employed instead of PPh3, poor yields were observed. In contrast, other mono-dentate ligand such as TFP Table 1. Optimization of reaction conditions.a
(Entry 7), PCy3 (Entry 8) and SPhos (Entry 11) behaved similarly to PPh3, while the use of XPhos27 (Entry 12) increased the yield of 3aa to 84%. In addition, the palladium catalyst loading could be lowered to 5 mol% (ligand loading was reduced to 11 mol% correspondingly) without undermining the overall yield (Entry 13). In this case, the product was obtained in 80% yield. Further optimizations regarding to base, solvent and palladium catalyst did not provide significant improvement in the efficiency (see the Supporting Information (SI) for details). A lower loading of base, was nevertheless, found to be beneficial. Thus, the optimized conditions utilized 2.5 equivalents of K2CO3 and furnished 3aa in 84% yield (81% isolated yield) (Entry 14). Intriguingly, replacement of 2a with (Z)-6-bromo-3-methylhex-2-en-1-ol (2a’)23 provides 3aa in a slightly lower yield (67% vs 81%) (see Table 2A), indicating the configuration of double bond in 2 impacts the efficiency of reaction. It is worthwhile mentioning that the prior works in Catellani-type reactions often enlisted NBE mediators in stoichiometric or superstoichiometric quantities.15,28 4 Conversely, herein 20 mol% of N was demonstrated to be sufficient enough. Meanwhile, employing N4 as a catalytic mediator leads to much cleaner reactions (less side reactions)29 and ease of purification since N4 can be removed with a simple basic aqueous solution during work up. 19d Table 2 outlines the application of the optimized conditions to probe the scope of aryl iodide. Aryl iodides containing electron-donating and -withdrawing groups all proved to be competent substrates to react with 2a, providing the desired tetrahydronaphthalenes in 48-88% yields. The reaction system also exhibited high chemo-selectivity: various functional groups were tolerated, including fluoro (3ea, 3ja and 3ka), chloro (3fa, 3oa and 3sa),30 bromo (3la and 3pa),30 benzyloxy (3ga), Boc-protected amino (3oa), TBS-protected Table 2. Reaction scope with respect to the Aryl iodide.a
Entry 1 2 3 4 5 6 7 8 9 10 11 12 13e 14e,f
Ligand PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 TFP PCy3 DPPE BINAP SPhos XPhos XPhos XPhos
[NBE] N1c N2c N3c N4c N5c N4 N4 N4 N4 N4 N4 N4 N4 N4
Yield [%]b 37 36 14 91 trace 77 (79)d 78 72 34 15 75 84 80 84 (81)g
aThe reaction
was performed on 0.1 mmol scale. bGC yield with 1,1’-biphenyl as an internal standard. c50 mol% was applied. dResult of pure endo-type 5-norbornene-2-carboxylic acid in parentheses. ewith 5 mol% of [Pd(C3H5)Cl]2, and 11 mol% of ligand. f2.5 equivalents of K2CO3 were applied. gIsolated yield in parentheses. TFP = tris(2-furyl)phosphine, DPPE = 1,2bis(diphenyl-phosphino)-ethane, Cy = cyclohexyl, BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl.
aAll
reactions were performed on 0.2 mmol scale. Isolated yields are reported. b2a’ was used instead of 2a. c(E)-6-iodo-3methylhex-2-en-1-ol (2a’’) was used instead of 2a. dwith 10 mol% of [Pd(C3H5)Cl]2, and 22 mol% of XPhos. TBS: tbutyldimethylsilyl, TBDPS: t-butyldiphenylsilyl.
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ACS Catalysis hydroxymethyl (3ia), ester (3na), and nitro (3ma) groups, providing handles for further product diversifications. Polycyclic products 3pa–sa were obtained in moderate to good yields (53–75%) when bicyclic aryl iodides 1p–s were used. Interestingly, meta-substituted aryl iodides 3benzyloxyiodobenzene (1t and 1u) could react with (E)-6-iodo3-methylhex-2-en-1-ol (2a’’, the iodo congener of 2a)31 to furnish the desired product 3ta and 3ua in 53% and 48% yield respectively. Notably, heteroaryl iodides 1v and 1w were suitable substrates, wherein their coupling with 2a afforded 3va and 3wa in 62% and 65% yield respectively. Moreover, the use of densely functionalized aryl iodides 1x and 1y as starting materials led to products 3xa and 3ya in high yields. Other alkylating reagents 2b‒d (homolog of 2a, different in the length of carbon chain) were also examined (Table 2). Similar to 2a, the reactions of aryl iodides 1 with 2b led to the desired tetrahydronaphthalene products (3ab, 3hb and 3xb) in good yields (61–75%) (Table 2A). In addition, 2c coupled smoothly with 1 to afford the indane-type products (3ac, 3bc–hc), albeit in slightly lower yields (41–56%) compared to 2a (Table 2B). As for 2d, the cascade reaction with 1a also proceeded smoothly to provide the corresponding product 3ad in 60% yield (Table 2B).
The scope of the alkylating reagents 2 was examined next. As illustrated in Table 3, subjecting the methyl ether 2A (R3 = Me) under the standard reaction conditions afforded the product enol ether 3A as a mixture of geometrical isomers in 81% yield (E:Z = 1.8:1). In the case of secondary allylic alcohols 2B–D (R2 = Me, n-Bu, and allyl), the corresponding ketone products 3B to 3D were obtained in 45–71% yields. Interestingly, the allylic alcohol 2D afforded the thermodynamically more stable α,β-unsaturated ketone 3D, wherein a concurrent double bond migration occurred. In addition to methyl group, alkylating agents bearing other olefinic substituents (R1), such as ethyl (2E), phenyl (2F), and hydrogen (2G) furnish the corresponding products 3E–G in good yields (67–81%). Gratifyingly, the protocol also proved effective for the construction of seven-membered rings, whose construction has proven more challenging compared to the five and sixmembered congeners.32 To this end, both the carbo and oxygentethered alkylating reagents 2H and 2I were employed, affording the 7-membered ring products 3H (76%) and 3I (21%) respectively. The relatively low yield for the latter was attributed to a completing retro-oxa-Michael addition,33 as the ring opened product 3I’ was obtained in 44% yield.
Scheme 1. Scale-up experiment and synthetic application.
unambiguously assigned by X-ray crystallographic analysis (CCDC: 1545854). In addition, the carbonyl group introduced during this Catellani/redox-relay Heck cascade offers a handle for rapid diversifications (see SI, Part 10 for details). Furthermore, the synthetic utilities of the above cascade was demonstrated through a short total synthesis of the benzomorphan-type analgesic drug eptazocine. As shown in Scheme 1B, readily available 1-(benzyloxy)-3-iodobenzene 1t and 2a’’ were subjected to the standard reaction conditions to afford the desired aldehyde 3ta in 53% yield, which was readily transformed to the secondary amine 4 via a facile reductive amination in 94% yield. The construction of the tricyclic key intermediate 5 was then realized through a “one-pot” cascade process, involving the chromium trioxide mediated benzylic CH bond oxidation34 followed by a Mannich reaction10a to give 5 in 71% overall yield. Debenzylation of 5 using Pd/C in acidic media under 40 atm H2 at 65 oC resulted in simultaneous reduction of the carbonyl group35 to afford the racemic eptazocine 6 in 90% yield. The analytical data of the synthetic material were identical to those of an authentic sample.36 To the best of our knowledge, this 4-step process represents the shortest synthesis of eptazocine to date.5,10a,37 Scheme 2. Preliminary asymmetric studies.
Table 3. Reaction scope with respect to the alkylating reagent.a
aGC
a
All reactions were performed on 0.2 mmol scale. Isolated yields are reported.
The practicality and robustness of this cascade process are evident from the 4.0 mmol scale experiment depicted in Scheme 1A, wherein application of the standard reaction conditions afforded 3xa in 73% yield (1.34 g). The structure of 3xa was
yield with biphenyl as an internal standard. bIsolated yield.
The asymmetric version of this Catellani/redox-relay Heck 38 Isolated yield. [a] GC yield withalso 1,1’-biphenyl as an internal standard. cascade was investigated (Scheme 2).[b] Screening of several commercially available chiral phosphine ligands as well as the chiral pyridine oxazoline ligands20 showcased that Carreira ligand L*39 can provide a moderate enantioselectivity for product 3aa (40% ee, 58% yield). Besides ligand, it is found that the mediator also played a pivotal role for stereocontrol. For example, while N1 and N6 were used as mediators instead of N4, 50% ee and 62% ee were obtained respectively, albeit in a lower yield. Gratifyingly, the product 3G was afforded in 78% ee (27% yield) using N6 as the mediator (see SI, Part 11 for details). To the best of our knowledge, this case represents the
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second example of catalytically asymmetric Catellani-type reaction.38 Efforts towards more generalized and efficient catalytic asymmetric systems are underway.
In summary, we have developed a cooperative catalyst comprising a Pd/XPhos complex and 5-norbornene-2carboxylic acid to achieve the concise synthesis of tetrahydronaphthalene and indane scaffolds via consecutive Catellani-type C-H activation and intramolecular redox-relay Heck reaction. 5-Norbornene-2-carboxylic acid acts as a catalytic mediator for the process, in a sub-stochiometric quantity of only 20 mol%. The cascade sequence enables the formation of two C-C bonds, the creation of a benzylic quaternary center, and the installation of a diversifiable carbonyl functionality in a single operation. This method offers broad synthetic utility for further elaborations, as exemplified by a 4-step total synthesis of the opioid analgesic eptazocine. Preliminary studies underscore of feasibility of an asymmetric Catellani/redox-relay Heck cascade – studies are ongoing to establish efficient and generalized conditions for this enantioselective transformation. Efforts to exploit this reaction in the total synthesis of complex natural products are underway in our laboratory.
Supporting Information Experimental procedures, characterization data for all new compounds, and crystallographic data (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.
Corresponding Author *E-mail:
[email protected] ‡These
authors contributed equally to this paper.
The authors declare no competing financial interests.
We are grateful to National “1000-Youth Talents Plan”, and the Innovation Team Program of Wuhan University (Program No. 2042017kf0232) for financial support. We thank Dr. Hengjiang Cong for X-ray analysis, Shenzhen Main Luck Pharmaceuticals Inc. for a generous donation of eptazocine•HBr, Prof. Phil S. Baran and Prof. Wenbo Liu for helpful discussions, Dr. Han-Qing Dong (Arvinas Inc., US), Dr. Ming Yan (the Scripps Research Institute, US) and Prof. P. Andrew Evans (Queen’s University) for assistance with the preparation of the manuscript.
(1) Roll, D. M.; Scheuer, P. J.; Matsumoto, G. K.; Clardy, J. Halenaquinone, a Pentacyclic Polyketide from a Marine Sponge. J. Am. Chem. Soc. 1983, 105, 6177–6178. (2) (a) Brian, P. W.; McGowan, J. G. Viridin: a Highly Fungistatic Substance Produced by Trichoderma Viride. Nature 1945, 156, 144– 145. (b) MacMillan, J.; Vanstone, A. E.; Yeboah, S. K. The Structure of Wortmannin, a Steroidal Fungal Metabolite. Chem. Commun. 1968,
Page 4 of 6
613–614. (c) Hanson, J. R. The Viridin Family of Steroidal Antibiotics. Nat. Prod. Rep. 1995, 12, 381–384. (3) Bercht, C. A. L.; Van Dongen, J. P. C. M.; Heerma, W.; Lousberg, R. J. J. C.; Küppers, F. J. E. M. Cannabispirone and Cannabispirenone, Two Naturally Occurring Spiro-Compounds. Tetrahedron 1976, 32, 2939–2943. (4) Garrido, L.; Zubía, E.; Ortega, M. J.; Salvá, J. Haouamines A and B: a New Class of Alkaloids from the Ascidian Aplidium Haouarianum. J. Org. Chem. 2003, 68, 293–299. (5) Shiotani, S.; Kometani, T.; Mitsuhashi, K.; Nozawa, T.; Kurobe, A.; Futsukaichi, O. 10-Hydroxy-4-Methyl-2,3,4,5,6,7-Hexahydro-1,6Methano-1H-4-Benzazonine Derivatives (Homobenzomorphans) as Analgesics. J. Med. Chem. 1976, 19, 803–806. (6) Smethurst, P. W.; Forrest, W. H.; Hayden, J. The Respiratory Effects of a Potent Analgesic (GPA 2087) in Man. Br. J. Anaesth. 1971, 43, 1129–1135. (7) (a) Basavaiah, D.; Bakthadoss, M.; Reddy, G. J. The First Intramolecular Friedel–Crafts Reaction of Baylis–Hillman Adducts: Synthesis of Functionalized Indene and Indane Derivatives. Synthesis 2001, 919–923. (b) Kurteva, V. B.; Santos, A. G.; Afonso, C. A. M. Microwave Accelerated Facile Synthesis of Fused Polynuclear Hydrocarbons in Dry Media by Intramolecular Friedel–Crafts Alkylation. Org. Biomol. Chem. 2004, 2, 514–523. (8) Tanaka, K.; Sawada, Y.; Aida, Y.; Thammathevo, M.; Tanaka, R.; Sagae, H.; Otake, Y. Rhodium-Catalyzed Convenient Synthesis of Functionalized Tetrahydronaphthalenes. Tetrahedron 2010, 66, 1563– 1569. (9) (a) Grisé, C. M.; Barriault, L. Gold-Catalyzed Synthesis of Substituted Tetrahydronaphthalenes. Org. Lett. 2006, 8, 5905–5908. (b) Grisé, C. M.; Rodrigue, E. M.; Barriault, L. Gold(I)-Catalyzed Benzannulation of 3-Hydroxy-1,5-Enynes: an Efficient Synthesis of Substituted Tetrahydronaphthalenes and Related Compounds. Tetrahedron 2008, 64, 797–808. (10) For selected examples, see: (a) Takemoto, T.; Sodeoka, M.; Sasai, H.; Shibasaki, M. Catalytic Asymmetric Synthesis of Benzylic Quaternary Carbon Centers. An Efficient Synthesis of (‒)-Eptazocine. J. Am. Chem. Soc. 1993, 115, 8477–8478. (b) Hirai, G.; Koizumi, Y.; Moharram, S. M.; Oguri, H.; Hirama, M. Construction of the Benzylic Quaternary Carbon Center of Zoanthenol by Intramolecular Mizoroki−Heck Reaction of Enone. Org. Lett. 2002, 4, 1627–1630. (c) Kesavan, S.; Panek, J. S.; Porco, J. A. Preparation of Alkylidene Indane and Related Scaffolds and Their Further Elaboration to Novel Chemotypes. Org. Lett. 2007, 9, 5203–5206. (11) For selected examples, see: (a) Kuo, C.-W.; Fang, J.-M. Synthesis of Xanthenes, Indanes, and Tetrahydronaphthalenes via Intramolecular Phenyl-Carbonyl Coupling Reactions. Synth. Commun. 2006, 31, 877– 892. (b) Kong, W.; Fuentes, N.; Garca-Domnguez, A.; Merino, E.; Nevado, C. Stereoselective Synthesis of Highly Functionalized Indanes and Dibenzocycloheptadienes through Complex Radical Cascade Reactions. Angew. Chem. Int . Ed. 2015, 54, 2487–2491. (12) The Overman group did excellent research on applying intramolecular Heck reaction for the construction of benzo-fused rings with a quaternary center. For selected works and reviews, see: (a) Abelman, M. M.; Overman, L. E.; Tran, V. D. Construction of Quaternary Carbon Centers by Palladium-Catalyzed Intramolecular Alkene Insertions. Total Synthesis of the Amaryllidaceae Alkaloids (±)-Tazettine and (±)-6a-Epipretazettine. J. Am. Chem. Soc. 1990, 112, 6959–6964. (b) Ashimori, A.; Overman, L. E. Catalytic Asymmetric Synthesis of Quaternary Carbon Centers. Palladium-Catalyzed Formation of Either Enantiomer of Spirooxindolesand Related Spirocyclics using a Single Enantiomer of a Chiral Diphosphine Ligand. J. Org. Chem. 1992, 57, 4571–4572. (c) Dounay, A. B.; Overman, L. E. The Asymmetric Intramolecular Heck Reaction in Natural Product Total Synthesis. Chem. Rev. 2003, 103, 2945–2964. (d) Douglas, C. J.; Overman, L. E. Catalytic Asymmetric Synthesis of All-Carbon Quaternary Stereocenters. Proc. Natl. Acad. Sci. USA 2004, 101, 5363– 5367. (13) Zhang, A.; RajanBabu, T. V. All-Carbon Quaternary Centers via Catalytic Asymmetric Hydrovinylation. New Approaches to the Exocyclic Side Chain Stereochemistry Problem. J. Am. Chem. Soc. 2006, 128, 5620–5621.
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ACS Catalysis (14) Matsuda, T.; Shigeno, M.; Makino, M.; Murakami, M. Enantioselective C−C Bond Cleavage Creating Chiral Quaternary Carbon Centers. Org. Lett. 2006, 8, 3379–3381. (15) For seminal work: Catellani, M.; Frignani, F.; Rangoni, A. A Complex Catalytic Cycle Leading to a Regioselective Synthesis of o,o′ -Disubstituted Vinylarenes. Angew. Chem. Int. Ed. 1997, 36, 119–122. For selected reviews, see: (a) Catellani, M. Novel Methods of Aromatic Functionalization Using Palladium and Norbornene as a Unique Catalytic System. Top. Organomet. Chem. 2005, 14, 21–53. (b) Lautens, M.; Alberico, D.; Bressy, C.; Fang, Y.-Q.; Mariampillai, B.; Wilhelm, T. Palladium-Catalyzed Ring-Forming Reactions: Methods and Applications. Pure Appl. Chem. 2006, 78, 351–361. (c) Catellani, M.; Motti, E.; Della Ca’, N. Catalytic Sequential Reactions Involving Palladacycle-Directed Aryl Coupling Steps. Acc. Chem. Res. 2008, 41, 1512–1522. (d) Martins, A.; Mariampillai, B.; Lautens, M. Synthesis in the Key of Catellani: Norbornene-Mediated ortho C–H Functionalization. Top. Curr. Chem. 2010, 292, 1–33. (e) Ferraccioli, R. Palladium-Catalyzed Synthesis of Carbo- and Heterocycles through Norbornene-Mediated ortho C–H Functionalization. Synthesis 2013, 45, 581–591. (f) Ye, J.; Lautens, M. Palladium-Catalysed NorborneneMediated C–H Functionalization of Arenes. Nat. Chem. 2015, 7, 863– 870. (g) Zhu, H.; Ye, C.; Chen, Z. Recent Advances in the Norbornene Mediated Palladium-Catalyzed Domino-type Catellani Reaction. Chin. J. Org. Chem. 2015, 35, 2291–2300. (h) Ca’, N. D.; Fontana, M.; Motti, E.; Catellani, M. Pd/Norbornene: a Winning Combination for Selective Aromatic Functionalization via C–H Bond Activation. Acc. Chem. Res. 2016, 49, 1389–1400. (i) Kim, D.-S.; Park, W.-J.; Jun, C.-H. Metal– Organic Cooperative Catalysis in C–H and C–C Bond Activation. Chem. Rev. 2017, 117, 8977–9015. (16) For mechanism studies on Catellani-type reactions, see: (a) Catellani, M.; Cugini, F.; Bocelli, G. Palladium-Catalyzed Sequential Reactions: a New Termination Step Leading to Spirocyclohexadienone Formation from p-Iodophenol and Bicyclo[2.2.1]Heptene. J. Organomet. Chem. 1999, 584, 63–67. (b) Cárdenas, D. J.; MartínMatute, B.; Echavarren, A. M. Aryl Transfer Between Pd(II) Centers or Pd(IV) Intermediates in Pd-catalyzed Domino Reactions. J. Am. Chem. Soc. 2006, 128, 5033–5040. (c) Larraufie, M.-H.; Maestri, G.; Beaume, A.; Derat, É.; Ollivier, C.; Fensterbank, L.; Courillon, C.; Lacôte, E.; Catellani, M.; Malacria, M. Exception to the ortho Effect in Palladium/Norbornene Catalysis. Angew. Chem. Int. Ed. 2011, 50, 12253–12256. (d) Maestri, G.; Motti, E.; Ca’, N. D.; Malacria, M.; Derat, E.; Catellani, M. Of the ortho Effect in Palladium/NorborneneCatalyzed Reactions: a Theoretical Investigation. J. Am. Chem. Soc. 2011, 133, 8574–8585. (e) Chai, D. I.; Thansandote, P.; Lautens, M. Mechanistic Studies of Pd-Catalyzed Regioselective Aryl C–H Bond Functionalization with Strained Alkenes: Origin of Regioselectivity. Chem. Eur. J. 2011, 17, 8175–8188. (17) For selected works, see: (a) Lautens, M.; Piguel, S. A New Route to Fused Aromatic Compounds by Using a Palladium-Catalyzed Alkylation –Alkenylation Sequence. Angew. Chem. Int. Ed. 2000, 39, 1045–1046. (b) Bressy, C.; Alberico, D.; Lautens, M. A Route to Annulated Indoles via a Palladium-Catalyzed Tandem Alkylation/Direct Arylation Reaction. J. Am. Chem. Soc. 2005, 127, 13148–13149. (c) Rudolph, A.; Rackelmann, N.; Lautens, M. Stereochemical and Mechanistic Investigations of a PalladiumCatalyzed Annulation of Secondary Alkyl Iodides. Angew. Chem. Int. Ed. 2007, 46, 1485–1488. (d) Gericke, K. M.; Chai, D. I.; Bieler, N.; Lautens, M. The Norbornene Shuttle: Multicomponent Domino Synthesis of Tetrasubstituted Helical Alkenes through Multiple C–H Functionalization. Angew. Chem. Int. Ed. 2009, 48, 1447–1451. (e) Candito, D. A.; Lautens, M. Palladium-Catalyzed Domino Direct Arylation/N-Arylation: Convenient Synthesis of Phenanthridines. Angew. Chem. Int. Ed. 2009, 48, 6713–6716. (f) Liu, H.; El- Salfiti, M.; Lautens, M. Expeditious Synthesis of Tetrasubstituted Helical Alkenes by a Cascade of Palladium-Catalyzed C–H Activations. Angew. Chem. Int. Ed. 2012, 51, 9846–9850. (18) For selected works, see: (a) Ferraccioli, R.; Carenzi, D.; Rombolà, O.; Catellani, M. Synthesis of 6-Phenanthridinones and Their Heterocyclic Analogues through Palladium-Catalyzed Sequential Aryl−Aryl and N-Aryl Coupling. Org. Lett. 2004, 6, 4759–4762. (b)
Motti, E.; Faccini, F.; Ferrari, I.; Catellani, M.; Ferraccioli, R. Sequential Unsymmetrical Aryl Coupling of o-Substituted Aryl Iodides with o-Bromophenols and Reaction with Olefins: Palladium-Catalyzed Synthesis of 6H-Dibenzopyran Derivatives. Org. Lett. 2006, 8, 3967– 3970. (c) Ca', N. D.; Motti, E.; Catellani, M. Palladium-Catalyzed Synthesis of Selectively Substituted Phenanthridine Derivatives. Adv. Synth. Catal. 2008, 350, 2513–2516. (d) Motti, E.; Ca', N. D.; Xu, D.; Piersimoni, A.; Bedogni, E.; Zhou, Z.-M.; Catellani, M. A Sequential Pd/Norbornene-Catalyzed Process Generates o-Biaryl Carbaldehydes or Ketones via a Redox Reaction or 6H‑ Dibenzopyrans by C–O Ring Closure. Org. Lett. 2012, 14, 5792–5795. (e) Xu, D.; Dai, L.; Catellani, M.; Motti, E.; Ca’, N. D.; Zhou, Z. A Novel Enantioselective Synthesis of 6H-Dibenzopyran Derivatives by Combined Palladium/Norbornene and Cinchona Alkaloid Catalysis. Org. Biomol. Chem. 2015, 13, 2260– 2263. (19) For selected examples, see: (a) Narbonne, V.; Retailleau, P.; Maestri, G.; Malacria, M. Diastereoselective Synthesis of Dibenzoazepines through Chelation on Palladium(IV) Intermediates. Org. Lett. 2014, 16, 628–631. (b) Wu, X.-X.; Shen, Y.; Chen, W.-L.; Chen, S.; Xu, P.-F.; Liang, Y.-M. Palladium-Catalyzed Dearomative Cyclization By a Norbornene-Mediated Sequence: A Route to Spiroindolenine Derivatives. Chem. Commun. 2015, 51, 16798–16801. (c) Li, R.; Dong, G. Direct Annulation between Aryl Iodides and Epoxides through Palladium/Norbornene Cooperative Catalysis. Angew. Chem. Int. Ed. 2018, 57, 1697–1701. (d) Cheng, H.-G.; Wu, C.; Chen, H.; Chen, R.; Qian, G.; Geng, Z.; Wei, Q.; Xia, Y.; Zhang, J.; Zhang, Y.; Zhou, Q. Epoxides as Alkylating Reagents for the Catellani Reaction. Angew. Chem. Int. Ed. 2018, 57, 3444–3448. (20) For selected works, see: (a) Werner, E. W.; Mei, T.-S.; Burckle, A. J.; Sigman, M. S. Enantioselective Heck Arylations of Acyclic Alkenyl Alcohols Using a Redox-Relay Strategy. Science 2012, 338, 1455–1458. (b) Mei, T.-S.; Werner, E. W.; Burckle, A. J.; Sigman, M. S. Enantioselective Redox-Relay Oxidative Heck Arylations of Acyclic Alkenyl Alcohols using Boronic Acids. J. Am. Chem. Soc. 2013, 135, 6830–6833. (c) Mei, T.-S.; Patel, H. H.; Sigman, M. S. Enantioselective Construction of Remote Quaternary Stereocentres. Nature 2014, 508, 340–344. (d) Patel, H. H.; Sigman, M. S. PalladiumCatalyzed Enantioselective Heck Alkenylation of Acyclic Alkenols Using a Redox-Relay Strategy. J. Am. Chem. Soc. 2015, 137, 3462– 3465. (e) Chen, Z.-M.; Nervig, C. S.; DeLuca, R. J.; Sigman, M. S. Palladium-Catalyzed Enantioselective Redox-Relay Heck Alkynylation of Alkenols to Access Propargylic Stereocenters. Angew. Chem. Int. Ed. 2017, 56, 6651–6654. (21) For an early related work, see: Catellani, M.; Deledda, S.; Ganchegui, B.; Hénin, F.; Motti, E.; Muzart, J. A New Catalytic Method for the Synthesis of Selectively Substituted Biphenyls Containing an Oxoalkyl Chain. J. Organomet. Chem. 2003, 687, 473– 482. (22) The Gu group developed an elegant Catellani-type annulation to construct quaternary centers, see: (a) Sui, X.; Zhu, R.; Li, G.; Ma, X.; Gu, Z. Pd-Catalyzed Chemoselective Catellani Ortho-Arylation of Iodopyrroles: Rapid Total Synthesis of Rhazinal. J. Am. Chem. Soc. 2013, 135, 9318–9321. (b) Zhao, K.; Xu, S.; Pan, C.; Sui, X.; Gu, Z. Catalytically Asymmetric Pd/Norbornene Catalysis: Enantioselective Synthesis of (+)-Rhazinal, (+)-Rhazinilam, and (+)Kopsiyunnanine C1−3. Org. Lett. 2016, 18, 3782–3785. (23) Miller, D. J.; Yu, F.; Knight, D. W.; Allemann, R. K. 6- and 14Fluoro Farnesyl Diphosphate: Mechanistic Probes for the Reaction Catalysed by Aristolochene Synthase. Org. Biomol. Chem. 2009, 7, 962–975. (24) Dong, Z.; Wang, J.; Ren, Z.; Dong, G. Ortho C–H Acylation of Aryl Iodides by Palladium/Norbornene Catalysis. Angew. Chem. Int. Ed. 2015, 54, 12664–12668. (25) Shen, P.-X.; Wang, X.-C.; Wang, P.; Zhu, R.-Y.; Yu, J.-Q. Ligand-Enabled meta-C−H Alkylation and Arylation Using a Modified Norbornene. J. Am. Chem. Soc. 2015, 137, 11574–11577. (26) The commercial available N4 is an endo/exo mixture (endo/exo = 4:1, as checked by 1H-NMR), which was used directly (The price of 5norbornene-2-carboxylic acid is US$ 0.8/gram (from Adamas)) (The potassium salt of N4 was also used as a mediator, see Ref. (19d)). For comparison, the pure endo-type 5-norbornene-2-carboxylic acid was
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synthesized according to the literatures: (a) Davies, D. I.; Gomez, P. M.; Hallett, P. Synthesis of 2,5- and 2,6-Norbornane Derivatives with Prostaglandin-Like Side Chains. J. Chem. Soc. Perkin Trans. 1, 1984, 843–848. (b) Mamedov, E. G. Asymmetrical [4+2]-Cycloaddition of (-)-Menthyl Acrylate and (-)-Menthyl Methacrylate to Cyclopentadiene in the Presence of BBr3. Russian. J. Org. Chem. 2001, 37, 217–222. (27) Huang, X.; Anderson, K. W.; Zim, D.; Jiang, L.; Klapars, A.; Buchwald, S. L. Expanding Pd-Catalyzed C−N Bond-Forming Processes: The First Amidation of Aryl Sulfonates, Aqueous Amination, and Complementarity with Cu-Catalyzed Reactions. J. Am. Chem. Soc. 2003, 125, 6653–6655. (28) There’re very limited cases in Catellani-type reactions applying a catalytic amount of mediator. For selected examples, see: (a) Ca', N. D.; Sassi, G.; Catellani, M. A Direct Palladium-Catalyzed Route to Selectively Substituted Carbazoles through Sequential C–C and C–N Bond Formation: Synthesis of Carbazomycin A. Adv. Synth. Catal. 2008, 350, 2179–2182. (b) Catellani, M.; Motti, E.; Ca', N. D. New Protocols for the Synthesis of Condensed Heterocyclic Rings Through Palladium-Catalyzed Aryl Coupling Reactions. Top. Catal. 2010, 53, 991–996. (c) Dong, Z.; Dong, G. Ortho vs Ipso: Site-Selective Pd and Norbornene-Catalyzed Arene C−H Amination Using Aryl Halides. J. Am. Chem. Soc. 2013, 135, 18350–18353. (d) Tsukano, C.; Muto, N.; Enkhtaivan, I.; Takemoto, Y. Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)–H and C(sp2)–H Functionalization Reactions. Chem. Asian J. 2014, 9, 2628–2634. (e) Ding, Q.; Ye, S.; Cheng, G.; Wang, P.; Farmer, M. E.; Yu, J.-Q. Ligand-Enabled metaSelective C−H Arylation of Nosyl-Protected Phenethylamines, Benzylamines, and 2‑ Aryl Anilines. J. Am. Chem. Soc. 2017, 139, 417–425. Refs. (19a, c-d) and (24). (29) Multiple-NBE-insertion byproducts usually formed in the presence of excess NBE, see Ref. (19c) and (24). (30) Aryl chloride and bromide survived in this reaction, are actually reactive under the converntional Pd/XPhos conditions, see: Bruno, N. C.; Niljianskul, N.; Buchwald, S. L. N-Substituted 2Aminobiphenylpalladium Methanesulfonate Precatalysts and Their Use in C–C and C–N Cross-Couplings. J. Org. Chem. 2014, 79, 4161– 4166. and Ref. (25). (31) Temple, K. J.; Wright, E. N.; Fierke, C. A.; Gibbs, R. A. Synthesis of Non-Natural, Frame-Shifted Isoprenoid Diphosphate Analogues. Org. Lett. 2016, 18, 6038–6041. (32) Battiste, M. A.; Pelphrey, P. M.; Wright, D. L. The Cycloaddition Strategy for the Synthesis of Natural Products Containing Carbocyclic Seven-Membered Rings. Chem. Eur. J. 2006, 12, 3438–3447. (33) Nising, C. F.; Bräse, S. The Oxa-Michael Reaction: from Recent Developments to Applications in Natural Product Synthesis. Chem. Soc. Rev. 2008, 37, 1218–1228.
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(34) Bianco, G. G.; Ferraz, H. M. C.; Costa, A. M.; Costa-Lotufo, L. V.; Pessoa, C.; de Moraes, M. O.; Schrems, M. G.; Pfaltz, A.; Silva, L. F. (+)- and (‒)-Mutisianthol: First Total Synthesis, Absolute Configuration, and Antitumor Activity. J. Org. Chem. 2009, 74, 2561– 2566. (35) (a) Nichols, D. E.; Jacob, J. N.; Hoffman, A. J.; Kohli, J. D.; Glock, D. C(2)-Methylation Abolishes DA1 Dopamine Agonist Activity of 2Amino-6,7-Dihydroxy-1,2,3,4-Tetrahydronaphthalene (6,7-ADTN): Steric Intolerance by the Receptor. J. Med. Chem. 1984, 27, 1701–1705. (b) Yang, J.; Rérat, A.; Lim, Y. J.; Gosmini, C.; Yoshikai, N. CobaltCatalyzed Enantioand Diastereoselective Intramolecular Hydroacylation of Trisubstituted Alkenes. Angew. Chem. Int. Ed. 2017, 56, 2449–2453. (36) The authentic (‒)-eptazocine•HBr sample was received as a gift from Shenzhen Main Luck Pharmaceuticals Inc.. Its crystal structure was obtained in our lab, and CCDC 1568079 contains the supplementary crystallographic data for this paper. These data are provided free of charge from The Cambridge Crystallographic Data Centre. (37) (a) Hulme, A. N.; Henry, S. S.; Meyers, A. I. Asymmetric Synthesis of the Key Intermediates Leading to (-)-Aphanorphine and (-)-Eptazocine. J. Org. Chem. 1995, 60, 1265–1270. (b) Shiotani, S.; Okada, H.; Yamamoto, T.; Nakamata, K.; Adachi, J.; Nakamoto, H. Asymmetric Synthesis of (+)- and (-)-Eptazocine via an Enzymatic Reaction. Heterocycles 1996, 43, 113–126. (c) Fadel, A.; Arzel, P. Enzymatic Asymmetrisation of Prochiral α,α-Disubstituted-Malonates and -1,3-Propanediols: Formal Asymmetric Syntheses of (−)Aphanorphine and (+)-Eptazocine. Tetrahedron: Asymmetry 1997, 8, 371–374. (d) Taylor, S. K.; Ivanovic, M.; Simons, L. J.; Davis, M. M. An Efficient Asymmetric Synthesis of Key Intermediates in the Synthesis of Aphanorphine and Eptazocine. Tetrahedron: Asymmetry 2003, 14, 743–747.(e) Nakao, Y.; Ebata, S.; Yada, A.; Hiyama, T.; Ikawa, M.; Ogoshi, S. Intramolecular Arylcyanation of Alkenes Catalyzed by Nickel/AlMe2Cl. J. Am. Chem. Soc. 2008, 130, 12874– 12875. (f) Chen, Q.; Huo, X.; Yang, Z.; She, X. Asymmetric Syntheses of (−)-Pentazocine and (−)-Eptazocine through an Aza-Prins Cyclization. Chem. Asian J. 2012, 7, 2543–2546. (38) For chiral substrate induced asymmetric Pd/NBE catalysis, see: a) Qureshi, Z.; Schlundt, W.; Lautens, M. Introduction of Hindered Electrophiles via C–H Functionalization in a Palladium-Catalyzed Multicomponent Domino Reaction. Synthesis 2015, 47, 2446–2456. Refs. (17c) and (19c-d). For the first reported catalytically asymmetric Pd/NBE catalysis, see Ref (22b). (39) Defieber, C.; Ariger, M. A.; Moriel, P.; Carreira, E. M. IridiumCatalyzed Synthesis of Primary Allylic Amines from Allylic Alcohols: Sulfamic Acid as Ammonia Equivalent. Angew. Chem. Int. Ed. 2007, 46, 3139–3143.
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