Norbornene Chemistry: Synthesis of Norbornene

Article pubs.acs.org/joc

Cite This: J. Org. Chem. 2018, 83, 13930−13939

Palladium/Norbornene Chemistry: Synthesis of NorborneneContaining Arylsilanes Involving Double C−Si Bond Formation Yankun Xu, Xiaodong Liu, Wenqi Chen, Guobo Deng, Yun Liang,* and Yuan Yang* National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha, Hunan 410081, China

J. Org. Chem. 2018.83:13930-13939. Downloaded from pubs.acs.org by UNIV STRASBOURG on 11/16/18. For personal use only.

S Supporting Information *

ABSTRACT: A novel palladium-catalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane has been described, which allows the simultaneous construction of two C−Si bonds and one C−C bond. The method achieves ortho C−H functionalization of aryl halides through the formation of the five-membered palladacycle, leading to norbornene-containing arylsilanes.

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INTRODUCTION Palladium/norbornene chemistry represents an attractive and efficient strategy and has been widely employed in the synthesis of polysubstituted arenes and diverse heterocycles.1 Among them, considerable efforts have been devoted to the development of palladium/norbornene-catalyzed ortho C−H functionalization of aryl iodides (the Catellani reaction; Scheme 1, reaction 1).1−4 This type of reaction, which allows sequential functionalization of both the ortho- and ispoposition of aryl iodides, was initially found by Catellani,2 and significant progress was made in the past two decades by the groups of Catellani,1a,b Lautens,1c−e and others.3,4 Generally, the five-membered palladacycle, as the key intermediate of the reaction, is first formed by sequential oxidative addition of Pd(0) to the aryl C−I bond, insertion of the norbornene, and C−H bond activation. Subsequently, sequential reaction with electrophiles and nucleophiles gives straightforward access to polyfunctionalized arenes. Alternatively, palladium-catalyzed ortho C−H functionalization of aryl iodides using norbornene as the reaction substrate has also been reported.5−8 However, most of the efficient transformations have focused on C−C/ C−N bond formation (Scheme 1, reaction 2a)4,5 and multiple C−C bond formation (Scheme 1, reaction 2b).5,6 Very recently, two papers reported on transformation of C−H bond toward C−Si bond. The Cheng group devoloped a palladium-catalyzed ortho-silylation of aryl iodides/arylsilylation of oxanorbornadiene reaction for assembling functionalized (Z)-β-substituted vinylsilanes.9a The Zhang group described a single example of bissilyation of 2iodoanisole and NBE.15c To date, such methods for constructing a C−Si bond via a palladium-catalyzed threecomponent cascade reaction of aryl iodides with norbornene are rather rare. Organosilicon compounds not only are important synthetic intermediates in organic synthesis, but they also have extensive application in medicinal chemistry and materials science.10−12 © 2018 American Chemical Society

Recently, transition-metal-catalyzed C−H silylation has become a powerful tool for the synthesis of organosilicon compounds.13 Among the reported methods, the protocol which employed hexamethyldisilane as a trimethylsilyl source has attracted tremendous attention.14,15 On the basis of previous research progress and our ongoing interest in the cross-coupling reactions involving palladacycles,16 we thought of developing an efficient palladium/norbornene strategy, which uses hexamethyldisilane as a trimethylsilyl source to achieve construction of a C−Si bond, to assemble functionalized arylsilanes. Herein, we reported a new palladiumcatalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane for the synthesis of norbornene-containing arylsilanes (Scheme 1, reaction 2c).9b

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RESULTS AND DISCUSSION We initially investigated the three-component reaction of 2iodotoluene 1b with norbornene and hexamethyldisilane for optimizing the reaction conditions (Table 1). Delightedly, the norbornene-containing arylsilane 2b was obtained in a 75% yield in the presence of 10 mol % of Pd(OAc)2, 20 mol % of PPh3, and 5 equiv of K3PO4 in CH3CN at 120 °C under a nitrogen atmosphere (entry 1). Inspired by the result, a range of palladium catalysts, namely, Pd(OCOCF3)2, [PdCl(πallyl)]2, PdCl2, and Pd(dba)2, were tested, and all of them displayed catalytic activity but were less effective than Pd(OAc)2 (entries 2−5). The effect of P-ligands was subsequently screened. We found that ligand-free and a number of other ligands, including P(o-tolyl)3, S-Phos, PtBu3, Xantphos, and Dppp, exhibited lower efficiency (entries 7−11). Control experiments demonstrated that base is essential for the three-component reaction, which could not occur without base (entry 12). Performing the reaction with Received: September 3, 2018 Published: October 17, 2018 13930

DOI: 10.1021/acs.joc.8b02282 J. Org. Chem. 2018, 83, 13930−13939

Article

The Journal of Organic Chemistry Scheme 1. Palladium/Norbornene Chemistry

Table 1. Optimization of the Reaction Conditionsa

entry

catalyst

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21b 22c

Pd(OAc)2 Pd(OCOCF3)2 [PdCl(π-allyl)]2 PdCl2 Pd(dba)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2

ligand PPh3 PPh3 PPh3 PPh3 PPh3 P(o-tol)3 S-Phos Pt-Bu3 Xantphos Dppp PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 PPh3

base

solvent

yield

K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4

CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN CH3CN toluene DMF DMSO dioxane CH3CN CH3CN

75 62 57 44 32 40 58 33 32 49 62 ND 41 70 10 15 7 50 5 ND 83 75

K2CO3 Cs2CO3 KOAc LiOt-Bu K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4

other bases, such as K2CO3, Cs2CO3, KOAc, and LiOt-Bu, resulted in a lower yield (entries 13−16). Finally, solvents and reaction temperatures were examined, and the results showed that the reaction using CH3CN as a medium at 110 °C proved to be preferential (entries 17−22). Accordingly, the optimal reaction conditions were as follows: Pd(OAc)2 (10 mol %), PPh3 (20 mol %), and K3PO4 (5 equiv) in CH3CN at 110 °C under a nitrogen atmosphere. With the optimal reaction conditions in hand, we turned our attention to examining the substrate scope of the reaction with regard to aryl iodides 1 (Scheme 2). Iodobenzene 1a was initially investigated, and the desired product 2a was obtained in 57% yield. Then, a series of substituents, including electrondonating groups (Et, i-Pr, and OMe) and electron-withdrawing groups (F, Cl, and CF3), at the ortho-position on the aryl ring of aryl iodides were well tolerated under the standard conditions (2c−h). Other monosubstituted aryl iodides 1i−k with a 3-Me, 4-Me, or 4-F group could smoothly be converted into the corresponding products 2i−k in moderate yields. Importantly, disubstituted aryl iodides, such as 1-iodo-2,3dimethylbenzene 1l, 1-iodo-2,4-dimethylbenzene 1m, 4-fluoro1-iodo-2-methylbenzene 1n, and 4-chloro-2-fluoro-1-iodobenzene 1o, proved to be competent substrates, delivering the products 2l−o in 60−89% yields. The reaction of polycyclic aryl iodides could also afford the target products in 57 and 38% yields (2p and 2q), respectively. Notably, norbornenecontaining heteroarylsilanes 2r−t were synthesized in the presence of norbornene, hexametyldisilane, Pd(OAc)2, PPh3, and K3PO4. Next, the reaction was applicable to aryl bromides (Scheme 3). Gratifyingly, an array of aryl bromides bearing electrondonating groups (Me and OMe) or electron-withdrawing groups (F, Cl, and NO2) was viable for furnishing the corresponding products in moderate to excellent yields (2b, 2f, 2g, 2u, and 2v). For bromobenzene 3a, norbornene-containing

a 1b (0.1 mmol), NBE (0.2 mmol), TMS−TMS (0.2 mmol), catalyst (10 mol %), ligand (20 mol %), base (0.5 mmol), and solvent (1 mL) at 120 °C under a nitrogen atmosphere for 5 h. Yields of isolated are given. b110 °C. c100 °C.

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The Journal of Organic Chemistry Scheme 2. Variation of the Aryl Iodidesa

Scheme 4. Variation of the 2-Iodobiphenyls 4a

a

4 (0.2 mmol), NBE (0.4 mmol), TMS−TMS (0.4 mmol), Pd(OAc)2 (10 mol %), PPh3 (20 mol %), K3PO4 (1 mmol), and CH3CN (2 mL) at 110 °C under a nitrogen atmosphere for 5 h.

a


even 4′-CO2Me) delivered the products 5g−i in diminished yields. These results showed that the electronic nature of substituents on the 1′-phenyl had a significant effect on the reactivity. Importantly, with respect to 4-(2-iodophenyl)pyridine 4j, the desired product 5j was afforded in 57% yield. Finally, we investigated the reactivity of 2-bromobiphenyls (Scheme 5). The experimental results demonstrated that 2-

Scheme 3. Variation of the Aryl Bromidesa

Scheme 5. Variation of the 2-Bromobiphenyls 6a

a


phenylsilane 2a was also generated in 88% yield. Furthermore, when 1-bromonaphthalene and 2-bromothiophene were used, the products 2p and 2r were obtained in decreased yields. Our previous work15e and Zhang’s studies15a simultaneously achieved bissilyation of the 2 and 2′ positions of 2-iodo-1,1′biphenyls. Therefore, 2-iodo-1,1′-biphenyl 4a was further explored. However, the bissilyation product of the 2 and 2′ positions was not detected, and the corresponding product 5a was produced in 69% yield by sequence functionalization of the 2 and 3 positions of 2-iodo-1,1′-biphenyl. Encouraged by the result, a wide range of 2-iodobiphenyls 4b−j bearing a Me, OMe, F, Cl, or CO2Me group were screened (Scheme 4). Substrates 4b−d with 5-Me, 5-F, or 5-Cl smoothly translated into the target products 5b−5d in good yields. The structure of 5d was unambiguously confirmed by single-crystal X-ray analysis (CCDC 1872222). When 2-iodobiphenyls with electron-donating groups (2′-Me and 4′-OMe) were used, the corresponding products were obtained in 79 and 81% yields (5e and 5f), respectively. In contrast, 2-iodobiphenyls 4g−i having an electron-withdrawing group (3′-F, 4′-Cl, or

a


bromobiphenyls exhibited similar reactivity compared with 2iodobiphenyls. Both 2-bromo-1,1′-biphenyl and substituted 2bromobiphenyls with Me, OMe, F, or Cl could react with norbornene and hexamethyldisilane, furnishing the desired products in 25−81% yields (5a−c, 5f, and 5g). Further utilization of the products 2a and 5a was carried out, and the corresponding products 7 and 8 were afforded in excellent yields through selective iodination (Scheme 6, eqs 1 and 2).17 Notably, the reaction scale up to 5 mmol of 6a could also give the product 5a in a 76% yield (Scheme 6, eq 3). A possible mechanism is proposed on the basis of the previous reports and present results (Scheme 7). First, the intermediate A is formed by sequential oxidation addition of 13932


The Journal of Organic Chemistry

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Scheme 6. Utilization of the Products and Gram-Scale Experiment

Article

EXPERIMENTAL SECTION

General Information. 1H NMR and 13C{1H} NMR spectra were recorded on a Bruker 400 or 500 MHz advance spectrometer at room temperature in CDCl3 with tetramethylsilane as the internal standard. Chemical shifts (δ) are reported in ppm, and coupling constants (J) are in Hertz (Hz). Multiplicities are reported using the following abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet. High-resolution mass spectra (HRMS) were recorded on an Agilent 1290 or GCT Premier Mass Spectrometer using ESI-TOF or EI (electrospray ionization time of flight). Reactions were monitored by thin-layer chromatography. Column chromatography (petroleum ether/ethyl acetate) was performed on silica gel (200−300 mesh). Analytical grade solvents and commercially available reagents were purchased from commercial sources and used directly without further purification unless otherwise stated. Typical Experimental Procedure for the Synthesis of 2Iodobiphenyls.15e,18a A 100 mL Schlenk tube was charged with substituted 2-iodoaniline (3.0 mmol, 1 equiv), substituted phenylboronic acid (3.9 mmol, 1.3 equiv), Pd(OAc)2 (0.15 mmol, 0.05 equiv), dppf (0.3 mmol, 0.1 equiv), Na2CO3 (12.0 mmol, 4 equiv), 1,4-dioxane (15.0 mL), and water (6.0 mL). The mixture was heated in an oil bath at 65 °C overnight. After the completion of the reaction, it was allowed to attain room temperature. Then, the reaction mixture was filtered and the filtrate diluted in ethyl acetate and washed with water. The combined organic layers were dried over anhydrous Na2SO4 and evaporated under a vacuum. The crude product was purified by silica gel column chromatography (petroleum ether/ EtOAc) to give the corresponding substituted 2-aminobiphenyls. A solution of concentrated HCl (36−38%; 2.7 mmol, 1.35 equiv, 1 mL) in water (4 mL) was added slowly to the prepared 2aminobiphenyl (2.0 mmol, 1 equiv) at 0 °C in portions. After stirring for 1 h at 0 °C, the aqueous solution of NaNO2 (3.0 mmol, 1.5 equiv) was added to the reaction mixture below 5 °C within 10 min and stirred for 1 h. Then, an aqueous solution of KI (4.0 mmol, 2 equiv) in water (4 mL) was added and the reaction mixture was stirred at room temperature overnight. After the completion of the reaction, saturated aqueous NaHCO3 was added to neutralize the acid and adjust the solution to pH > 7. Then, the residue was extracted into ethyl acetate (3 × 5 mL). The combined organic phases were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether unless otherwise noted) to give the desired 2-iodobiphenyls. Typical Experimental Procedure for the Synthesis of 2Bromobiphenyls.18b A 25 mL Schlenk tube was charged with substituted 1-bromo-2-iodobenzene (1.0 mmol, 1 equiv), substituted phenylboronic acid (1.05 mmol, 1.05 equiv), PdCl2(PPh3)2 (0.015 mmol, 0.015 equiv), K2CO3 (2.5 mmol, 2.5 equiv), DME (3 mL), and water (0.4 mL). The mixture was heated in an oil bath at 80 °C for 5 h. After the completion of the reaction, it was allowed to cool to r.t., DME was evaporated, and water (12 mL) and ether (8 mL) were added. The layers were separated, and the aqueous layer was extracted with diethyl ether (3 × 8 mL). The combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and evaporated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether unless otherwise noted) to give 2-bromobiphenyls. Typical Experimental Procedure for the Synthesis of 2 or 5. To a Schlenk tube were added aryl halides (0.2 mmol, 1 equiv), hexamethyldisilane (0.4 mmol, 2 equiv, 58.5 mg), norbornene (0.4 mmol, 2 equiv, 37.6 mg), Pd(OAc)2 (0.02 mmol, 0.1 equiv, 4.5 mg), PPh3 (0.04 mmol, 0.2 equiv, 10.5 mg), K3PO4 (1.0 mmol, 5 equiv, 212.3 mg), and CH3CN (2 mL). Then, the tube was charged with nitrogen and was stirred at 110 °C (oil bath temperature) for the indicated time until complete consumption of starting material, as monitored by TLC analysis. After the completion of the reaction, the resulting suspension was filtered and washed with ethyl acetate. The combined filtrates were concentrated under reduced pressure and purified via silica-gel column chromatography (petroleum ether/ethyl acetate) to give the desired product 2 or 5.

Scheme 7. Possible Reaction Mechanism

Pd(0) to the C−X bond and migration insertion of norbornene. Next, intermediate A undergoes intramolecular ortho C−H activation to afford the five-membered palladacycle B, which produces the intermediate C through the oxidative addition to hexamethyldisilane (path a). Subsequently, the first reductive elimination of intermediate C gives the intermediate D. Finally, intermediate D undergoes the second reductive elimination to furnish products 2 and 5 and regenerate Pd(0). Furthermore, the σ bond metathesis pathway involving intermediate F cannot be ruled out (path b).

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CONCLUSION In summary, this research reported the synthesis of diverse norbornene-containing arylsilanes from aryl halides, norbornene, and hexamethyldisilane via a palladium-catalyzed threecomponent cascade reaction. The method gave straightforward access to norbornene-containing arylsilanes with good functionalization tolerance in moderate to excellent yields. In the transformation, three chemical bonds, including two C−Si bonds and one C−C bond, were constructed. Further applications of the method are currently underway in our laboratory. 13933


Article


38.2 (d, J = 14.8 Hz), 33.0, 32.5 (d, J = 1.6 Hz), 1.3, −1.0 (d, J = 1.0 Hz). HRMS (EI) m/z calcd for C19H31FSi2+ (M)+ 334.1948, found 334.1951. (3-Chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)phenyl)trimethylsilane (2g). 2g (1g: 57.5 mg, 82%; 3g: 54.6 mg, 78%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.38 (d, J = 7.5 Hz, 1H), 7.31 (d, J = 7.5 Hz, 1H), 7.10−7.07 (m, 1H), 3.42 (d, J = 11.0 Hz, 1H), 2.82 (s, 1H), 2.39−2.35 (m, 2H), 1.87−1.83 (m, 1H), 1.62−1.57 (m, 1H), 1.46−1.40 (m, 2H), 1.38−1.34 (m, 1H), 1.32 (d, J = 10.0 Hz, 1H), 0.37 (s, 9H), −0.33 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 147.0, 145.0, 133.5, 133.0, 132.9, 126.7, 53.3, 45.1, 41.2, 40.1, 38.9, 33.3, 32.4, 1.8, −0.7. HRMS (EI) m/z calcd for C19H31ClSi2+ (M)+ 350.1653, found 350.1652. Trimethyl(3-(trifluoromethyl)-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane (2h). 2h (62.2 mg, 81%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.71 (d, J = 7.6 Hz, 2H), 7.26 (t, J = 7.6 Hz, 1H), 3.66 (d, J = 11.2 Hz, 1H), 2.37 (s, 1H), 2.89 (s, 1H), 1.99 (d, J = 10.0 Hz, 1H), 1.82 (d, J = 11.6 Hz, 1H), 1.62−1.58 (m, 1H), 1.52 (d, J = 11.6 Hz, 1H), 1.48−1.43 (m, 1H), 1.39−1.34 (m, 1H), 1.25 (d, J = 10.0 Hz, 1H), 0.41 (s, 9H), −0.41 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 150.0, 146.0, 139.1, 128.6 (q, J = 7.4 Hz), 127.8 (d, J = 30.2 Hz), 125.2, 124.7 (q, J = 271.0 Hz), 54.4, 44.9, 41.5 (q, J = 5.0 Hz), 39.3, 38.9 (q, J = 15.6 Hz), 34.3, 31.7, 2.4, −0.8. HRMS (EI) m/z calcd for C20H31F3Si2+ (M)+ 384.1916, found 384.1917. Trimethyl(4-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane (2i). 2i (41 mg, 62%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 86.8−93.0 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.32 (d, J = 7.5 Hz, 1H), 7.22 (s, 1H), 6.99 (d, J = 7.5 Hz, 1H), 3.16 (d, J = 10.5 Hz, 1H), 2.37−2.34 (m, 5H), 2.02 (d, J = 10.0 Hz, 1H), 1.80−1.76 (m, 1H), 1.64−1.59 (m, 1H), 1.46−1.36 (m, 3H), 1.28 (d, J = 10.0 Hz, 1H), 0.33 (s, 9H), −0.35 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 152.8, 138.8, 135.6, 134.3, 127.7, 125.9, 51.0, 44.9, 43.6, 39.0, 38.5, 32.8, 32.2, 21.4, 1.0, −0.8. HRMS (EI) m/z calcd for C20H34Si2+ (M)+ 330.2199, found 330.2195. Trimethyl(5-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane (2j). 2j (41.6 mg, 63%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.30 (d, J = 8.0 Hz, 1H), 7.21 (s, 1H), 7.12 (d, J = 7.5 Hz, 1H), 3.14 (d, J = 10.0 Hz, 1H), 2.36−2.32 (m, 5H), 1.98 (d, J = 9.5 Hz, 1H), 1.79−1.74 (m, 1H), 1.63−1.57 (m, 1H), 1.45−1.40 (m, 1H), 1.37−1.35 (m, 2H), 1.27− 1.25 (m, 1H), 0.34 (s, 9H), −0.34 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 149.7, 138.7, 134.8, 134.1, 130.0, 126.5, 50.7, 45.0, 43.5, 38.8, 38.5, 32.8, 32.1, 21.1, 1.0, −0.7. HRMS (EI) m/z calcd for C20H34Si2+ (M)+ 330.2199, found 330.2196. (5-Fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)phenyl)trimethylsilane (2k). 2k (34 mg, 51%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.36−7.34 (m, 1H), 7.08− 7.07 (m, 1H), 6.98−6.95 (m, 1H), 3.13 (d, J = 10.5 Hz, 1H), 2.36 (s, 1H), 2.28 (s, 1H), 1.93 (d, J = 10.0 Hz, 1H), 1.78−1.73 (m, 1H), 1.63−1.58 (m, 1H), 1.43−1.26 (m, 4H), 0.33 (s, 9H), −0.35 (s, 9H). 13 C{1H} NMR (125 MHz, CDCl3, δ ppm) 160.7 (d, J = 244.3 Hz), 148.4 (d, J = 2.8 Hz), 141.9 (d, J = 2.8 Hz), 128.0 (d, J = 6.3 Hz), 120.2 (d, J = 17.9 Hz), 115.6 (d, J = 21.1 Hz), 50.4, 45.0, 43.5, 38.7, 38.6, 32.7, 32.1, 0.7, −0.7. HRMS (ESI) m/z calcd for C19H31FSi2+ (M)+ 334.1948, found 334.1950. (3,4-Dimethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsilane (2l). 2l (58.6 mg, 85%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.27 (d, J = 7.2 Hz, 1H), 7.03 (d, J = 7.2 Hz, 1H), 3.52 (d, J = 10.8 Hz, 1H), 2.74 (s, 1H), 2.40 (s, 4H), 2.28 (s, 3H), 2.05 (d, J = 9.6 Hz, 1H), 1.87 (t, J = 11.6 Hz, 1H), 1.62−1.61 (m, 1H), 1.55−1.50 (m, 1H), 1.7−1.39 (m, 3H), 0.37 (s, 9H), −0.39 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 148.5, 139.7, 139.6, 134.4, 132.8, 127.3, 54.1, 45.1, 42.0, 40.1,

Trimethyl(2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)phenyl)silane (2a). 2a (1a: 36 mg, 57%; 3a: 55.7 mg, 88%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.42−7.40 (m, 2H), 7.33−7.29 (m, 1H), 7.17−7.14 (m, 1H), 3.17 (d, J = 10.5 Hz, 1H), 2.36 (dd, J = 3.5 Hz, 11.0 Hz, 2H), 1.99 (d, J = 10.0 Hz, 1H), 1.80−1.75 (m, 1H), 1.64−1.59 (m, 1H), 1.46−1.41 (m, 1H), 1.39− 1.34 (m, 2H), 1.29−1.27 (m, 1H), 0.34 (s, 9H), −0.35 (s, 9H). 13 C{1H} NMR (125 MHz, CDCl3, δ ppm) 152.7, 138.9, 134.2, 129.2, 126.6, 125.1, 51.1, 44.9, 43.5, 38.9, 38.5, 32.8, 32.2, 1.0, −0.8. HRMS (ESI-TOF) m/z calcd for C19H33Si2+ (M+H)+ 317.2115, found 317.2116. Trimethyl(3-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane (2b). 2b (1b: 54.7 mg, 83%; 3b: 54.7 mg, 83%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.40 (d, J = 5.0 Hz, 1H), 7.14−7.10 (m, 2H), 3.53 (d, J = 11.0 Hz, 1H), 2.75 (s, 1H), 2.56 (s, 3H), 2.42 (s, 1H), 2.04 (d, J = 9.5 Hz, 1H), 1.91−1.85 (m, 1H), 1.67−1.54 (m, 2H), 1.48 (d, J = 11.0 Hz, 1H), 1.45−1.38 (m, 2H), 0.41 (s, 9H), −0.34 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 148.5, 142.1, 135.2, 134.2, 133.1, 125.4, 53.9, 44.9, 41.0, 39.8, 38.9, 33.5, 32.2, 23.1, 2.1, −0.6. HRMS (EI) m/ z calcd for C20H34Si2+ (M)+ 330.2199, found 330.2196. (3-Ethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2yl)phenyl)trimethylsilane (2c). 2c (56.5 mg, 82%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.35−7.34 (m, 1H), 7.18− 7.17 (m, 1H), 7.15−7.12 (m, 1H), 3.47 (d, J = 11.0 Hz, 1H), 3.16− 3.09 (m, 1H), 2.63−2.56 (m, 2H), 2.38 (s, 1H), 2.01 (d, J = 9.5 Hz, 1H), 1.87−1.82 (m, 1H), 1.61−1.56 (m, 1H), 1.53−1.49 (m, 1H), 1.43 (d, J = 11.0 Hz, 1H), 1.40−1.36 (m, 2H), 1.24−1.21 (m, 3H), 0.36 (s, 9H), −0.42 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 147.7, 142.3, 141.9, 133.0, 131.9, 125.5, 53.6, 45.2, 41.7, 40.2, 38.8, 33.8, 31.9, 27.1, 17.3, 2.2, −0.8. HRMS (EI) m/z calcd for C21H36Si2+ (M)+ 344.2356, found 344.2356. (3-Isopropyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsilane (2d). 2d (46 mg, 64%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.37−7.31 (m, 2H), 7.18−7.14 (m, 1H), 3.60−3.52 (m, 2H), 2.68 (s, 1H), 2.39 (s, 1H), 1.97 (d, J = 12.0 Hz, 1H), 1.88−1.82 (m, 1H), 1.59 (m, 1H), 1.53−1.47 (m, 2H), 1.40 (d, J = 12.0 Hz, 2H), 1.34 (d, J = 8.0 Hz, 3H), 1.22 (d, J = 7.5 Hz, 3H), 0.38 (s, 9H), −0.36 (s, 9H). 13 C{1H}NMR (125 MHz, CDCl3, δ ppm) 147.4, 147.1, 142.5, 133.2, 128.0, 125.6, 53.8, 44.5, 42.0, 40.5, 39.2, 34.0, 31.9, 28.3, 27.9, 23.5, 2.4, −0.8. HRMS (EI) m/z calcd for C22H38Si2+ (M)+ 358.2512, found 358.2511. (3-Methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsilane (2e).12c 2e (45 mg, 65%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.18−7.15 (m, 1H), 7.07 (d, J = 7.0 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 3.74 (s, 3H), 3.22 (d, J = 10.5 Hz, 1H), 2.45 (m, 1H), 2.33 (m, 1H), 2.26 (d, J = 9.5 Hz, 1H), 1.83−1.78 (m, 1H), 1.56−1.51 (m, 1H), 1.44−1.40 (m, 1H), 1.34−1.27 (m, 2H), 1.18 (d, J = 9.0 Hz, 1H), 0.35 (s, 9H), −0.39 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 157.8, 142.3, 138.4, 126.8, 126.5, 112.2, 53.9, 51.6, 44.0, 42.6, 39.2, 38.7, 33.1, 32.7, 1.5, −0.9. HRMS (EI) m/z calcd for C20H34OSi2+ (M)+ 346.2148, found 358.2150. (3-Fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)phenyl)trimethylsilane (2f). 2f (1f: 55.5 mg, 83%; 3f: 60.2 mg, 90%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.26 (d, J = 7.2 Hz, 1H), 7.20−7.15 (m, 1H),7.04−7.00 (m, 1H), 3.24 (d, J = 10.4 Hz, 1H), 2.52 (s, 1H), 2.41 (s, 1H), 2.20 (d, J = 9.2 Hz, 1H), 1.87−1.82 (m, 1H), 1.67−1.61 (m, 1H), 1.48−1.43 (m, 1H), 1.36− 1.26 (m, 2H), 1.27 (d, J = 10.0 Hz, 1H), 0.39 (s, 9H), −0.30 (s, 9H). 13 C{1H} NMR (100 MHz, CDCl3, δ ppm) 161.3 (d, J = 246.4 Hz), 143.6 (d, J = 3.0 Hz), 137.0 (d, J = 12.1 Hz), 130.2 (d, J = 2.7 Hz), 127.1 (d, J = 7.9 Hz), 117.6 (d, J = 24.7 Hz), 50.1, 44.0, 42.8, 39.3, 13934


Article

The Journal of Organic Chemistry 38.9, 33.6, 32.3, 21.4, 17.7, 2.1, −0.7. HRMS (EI) m/z calcd for C21H36Si2+ (M)+ 344.2356, found 344.2357. (3,5-Dimethyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsilane (2m). 2m (61.3 mg, 89%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.11 (s, 1H), 6.88 (s, 1H), 3.43−3.41 (d, J = 10.8 Hz, 1H), 2.63 (s, 1H), 2.44 (s, 3H), 2.33 (s, 1H), 2.24 (s, 3H), 1.95 (d, J = 10.0 Hz, 1H), 1.83−1.77 (m, 1H), 1.59−1.53 (m, 1H), 1.48−1.43 (m, 1H), 1.40 (d, J = 11.2 Hz, 1H), 1.35−1.28 (m, 2H), 0.32 (s, 9H), −0.40 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 145.4, 141.9, 134.9, 134.8, 134.3, 133.8, 53.3, 44.9, 41.1, 39.7, 38.8, 33.5, 32.2, 23.0, 20.7, 2.1, 0.6. HRMS (EI) m/z calcd for C21H36Si2+ (M)+ 344.2356, found 344.2356. ((1R,2S,3S,4S)-3-(4-Fluoro-2-methyl-6-(trimethylsilyl)phenyl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane (2n). 2n (57.9 mg, 83%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.03 (d, J = 9.0 Hz, 1H), 6.79 (d, J = 9.0 Hz, 1H), 3.45 (d, J = 11.0 Hz, 1H), 2.65 (s, 1H), 2.50 (s, 3H), 2.37 (s, 1H), 1.96 (d, J = 9.5 Hz, 1H), 1.86−1.82 (m, 1H), 1.61−1.57 (m, 1H), 1.48−1.46 (m, 1H), 1.42 (d, J = 11.0 Hz, 1H), 1.35−1.34 (m, 2H), 0.36 (s, 9H), −0.35 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 160.6 (d, J = 244.5 Hz), 145.1 (d, J = 2.6 Hz), 144.2 (d, J = 2.6 Hz), 137.6 (d, J = 2.5 Hz), 119.8 (d, J = 19.8 Hz), 119.1 (d, J = 18.1 Hz), 53.1, 45.0, 41.1, 39.8, 38.9, 33.5, 32.2, 23.1, 1.8, −0.6. HRMS (EI) m/z calcd for C20H33FSi2+ (M+H)+ 348.2105, found 348.2101. ((1R,2S,3S,4S)-3-(4-Chloro-2-fluoro-6-(trimethylsilyl)phenyl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane (2o). 2o (44.5 mg, 60%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.18 (d, J = 2.0 Hz, 1H), 7.02 (dd, J = 1.5 Hz, 11.5 Hz, 1H), 3.16 (d, J = 11.0 Hz, 1H), 2.43−2.37 (m, 2H), 2.09 (d, J = 9.5 Hz, 1H), 1.81−1.77 (m, 1H), 1.62−1.57 (m, 1H), 1.41−1.37 (m, 1H), 1.33−1.26 (m, 2H), 1.22 (d, J = 10.0 Hz, 1H), 0.35 (s, 9H), −0.32 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 161.0 (d, J = 250.9 Hz), 145.5 (d, J = 3.8 Hz), 135.6 (d, J = 12.7 Hz), 131.9 (d, J = 9.0 Hz), 130.0 (d, J = 2.6 Hz), 117.8 (d, J = 28.1 Hz), 49.7 (d, J = 1.5 Hz), 44.0, 42.7 (d, J = 1.4 Hz), 39.2, 38.2 (d, J = 14.2 Hz), 33.0, 32.4, 1.0, −0.9. HRMS (EI) m/ z calcd for C19H30ClFSi2+ (M)+ 368.1559, found 368.1550. Trimethyl(1-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)naphthalen-2-yl)silane (2p). 2p (1p: 41.8 mg, 57%; 3p: 35,2 mg, 48%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 77.2−79.5 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 8.65 (d, J = 7.5 Hz, 1H), 7.82 (d, J = 7.0 Hz, 1H), 7.70 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.45− 7.44 (m, 2H), 3.85 (d, J = 11.0 Hz, 1H), 3.10 (s, 1H), 2.48 (s, 1H), 2.37 (d, J = 9.0 Hz, 1H), 1.98−1.93 (m, 1H), 1.73−1.72 (m, 1H), 1.64−1.62 (m, 1H), 1.60−1.58 (m, 1H), 1.49−1.47 (m, 2H), 0.46 (s 9H), −0.68 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 148.4, 139.0, 135.3, 132.4, 131.4, 128.6, 126.7, 126.1, 125.5, 124.4, 54.2, 45.7, 42.7, 40.4, 39.3, 34.0, 32.2, 2.1, −1.0. HRMS (EI) m/z calcd for C23H34Si2+ (M)+ 366.2199, found 366.2196. Trimethyl(3-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)naphthalen-2-yl)silane (2q). 2q (27.8 mg, 38%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.94 (s, 1H), 7.8 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 8..0 Hz, 1H), 7.48−7.40 (m, 2H), 3.30 (d, J = 10.0 Hz, 1H), 2.47 (dd, J = 3.0 Hz, 11.0 Hz, 2H), 2.20 (d, J = 10.0 Hz, 1H), 1.84−1.79 (m, 1H), 1.70−1.64 (m, 1H), 1.52−1.46 (m, 2H), 1.43−1−1.40 (m, 1H), 1.38 (dd, J = 2.0 Hz, 10.5 Hz, 1H), 0.44 (s, 9H), −0.39 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 149.7, 138.8, 134.7, 133.9, 131.3, 127.8, 127.1, 126.3, 125.0, 124.7, 51.0, 45.5, 44.0, 39.0, 38.7, 32.8, 32.2, 1.0, −0.7. HRMS (EI) m/z calcd for C23H34Si2+ (M)+ 366.2199, found 366.2194. Trimethyl(2-((1S,2R,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)thiophen-3-yl)silane (2r). 2r (1r: 33.0 mg, 51%; 3r: 25.8 mg, 40%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.11 (d, J = 5.0 Hz, 1H), 6.90 (d, J = 4.5 Hz, 1H), 3.50 (d, J = 10.0 Hz, 1H), 2.31 (d, J = 19.0 Hz, 2H), 1.90 (d, J = 9.5 Hz, 1H), 1.71−1.69 (m,

1H), 1.66−1.63 (m, 1H), 1.38−1.33 (m, 3H), 1.20 (d, J = 10.0 Hz, 1H), 0.29 (s, 9H), −0.23 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 157.9, 135.7, 131.4, 121.9, 48.3, 46.1, 41.9, 39.0, 37.6, 32.7, 31.2, 0.5, −1.1. HRMS (ESI-TOF) m/z calcd for C17H31SSi2+ (M +H)+ 323.1680, found 323.1684. Trimethyl(3-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)thiophen-2-yl)silane (2s). 2s (44.5 mg, 69%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.46 (d, J = 4.4 Hz, 1H), 7.19 (d, J = 4.4 Hz, 1H), 3.23 (d, J = 10.0 Hz, 1H), 2.36 (s, 1H), 2.25 (s, 1H), 1.89 (d, J = 9.6 Hz, 1H), 1.75−1.72 (m, 1H), 1.66−1.63 (m, 1H), 1.39−1.31 (m, 3H), 1.19 (d, J = 10.4 Hz, 1H), 0.36 (s, 9H), −0.28 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 154.1, 133.2, 129.7, 128.5, 47.4, 44.2, 41.7, 38.8, 37.8, 32.9, 31.7, 0.7, −0.9. HRMS (ESI-TOF) m/z calcd for C17H31SSi2+ (M+H)+ 323.1680, found 323.1681. 6-(Trimethylsilyl)-5-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)quinoline (2t). 2t (44.2 mg, 56%) was prepared according to the typical procedure (petroleum ether/ethyl acetate = 5:1) as a yellow solid. mp: 99.0−101 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 8.98 (d, J = 8.5 Hz, 1H), 8.86 (dd, J = 1.5 Hz, 4 Hz, 1H), 7.95 (d, J = 8.5 Hz, 1H), 7.80 (d, J = 8.5 Hz, 1H), 7.34−7.31 (m, 1H), 3.83 (d, J = 11.0 Hz, 1H), 3.00 (s, 1H), 2.47 (d, J = 4.0 Hz, 1H), 2.22 (d, J = 9.5 Hz, 1H), 1.96−1.89 (m, 1H), 1.73−1.67 (m, 1H), 1.62−1.56 (m, 2H), 1.48−1.42 (m, 2H), 0.43 (s, 9H), −0.71 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 149.8, 149.7, 140.0, 135.0, 134.8, 127.3, 127.1, 119.2, 53.8, 45.6, 42.8, 40.4, 39.4, 33.9, 32.1, 1.9, −1.0. HRMS (ESI-TOF) m/z calcd for C22H34NSi2+ (M +H)+ 368.2224, found 368.2227. (5-Methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)trimethylsilane (2u). 2u (48.5 mg, 70%) was prepared according to the typical procedure (petroleum ether/ethyl acetate = 100:1) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.33 (d, J = 9.0 Hz, 1H), 6.97 (d, J = 3.0 Hz, 1H), 6.85 (dd, J = 3.0 Hz, 9.0 Hz, 1H), 3.80 (s, 3H), 3.13 (d, J = 10.5 Hz, 1H), 2.37 (d, J = 3.5 Hz, 1H), 2.29 (d, J = 2.5 Hz, 1H), 1.96 (d, J = 9.5 Hz, 1H), 1.79−1.73 (m, 1H), 1.64−1.58 (m, 1H), 1.44−1.40 (m, 1H), 1.37− 1.32 (m, 2H), 1.26 (dd, J = 1.5 Hz, 10.5 Hz, 1H), 0.34 (s, 9H), −0.33 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 156.9, 145.0, 140.5, 127.6, 119.9, 113.8, 55.1, 50.3, 45.1, 43.5, 38.7, 38.6, 32.8, 32.1, 0.9, −0.7. HRMS (EI) m/z calcd for C20H34OSi2+ (M)+ 346.2148, found 346.2151. Trimethyl(5-nitro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)silane (2v). 2v (36.2 mg, 50%) was prepared according to the typical procedure (petroleum ether/ethyl acetate = 200:1) as a yellow solid. mp: 107.4−112.1 °C. 1H NMR (400 MHz, CDCl3, δ ppm) 8.25 (s, 1H), 8.13 (d, J = 8.8 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 3.25 (d, J = 10.4 Hz, 1H), 2.40 (s, 1H), 2.32 (s, 1H), 1.95 (d, J = 10.0 Hz, 1H), 1.82−1.76 (m, 1H), 1.67−1.64 (m, 1H), 1.44− 1.36 (m, 3H), 1.31 (d, J = 10.4 Hz, 1H), 0.39 (s, 9H), −0.35 (s, 9H). 13 C{1H} NMR (100 MHz, CDCl3, δ ppm) 160.7, 145.5, 141.7, 128.8, 127.4, 124.1, 51.4, 45.0, 43.5, 38.9, 38.6, 32.6, 32.1, 0.6, −0.7. HRMS (ESI-TOF) m/z calcd for C19H31NO2Si2Na+ (M+Na)+ 384.1786, found 384.1783. Trimethyl((1R,2S,3S,4S)-3-(3-(trimethylsilyl)-[1,1′-biphenyl]-2-yl)bicyclo[2.2.1]heptan-2-yl)silane (5a). 5a (4a: 54.2 mg, 69%; 6a: 62.0 mg, 79%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 87.9−91.0 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.51 (d, J = 7.0 Hz, 1H), 7.42 (d, J = 7.0 Hz, 1H), 7.38−7.30 (m, 3H), 7.28−7.26 (m, 1H), 7.17−7.14 (m, 1H), 7.03 (d, J = 7.0 Hz, 1H), 3.58 (d, J = 11.0 Hz, 1H), 2.65 (s, 1H), 2.00 (s, 1H), 1.63−1.58 (m, 1H), 1.49−1.44 (m, 1H), 1.35 (d, J = 11.0 Hz, 1H), 1.30−1.23 (m, 2H), 0.54 (d, J = 9.5 Hz, 1H), 0.42, (s, 9H), 0.35 (d, J = 9.0 Hz, 1H), −0.37 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 148.4, 144.4, 142.6, 141.3, 134.9, 134.5, 131.8, 129.8, 127.4, 126.6, 126.4, 124.4, 55.1, 43.8, 43.3, 38.7, 37.8, 33.0, 32.8, 2.1, −0.5. HRMS (EI) m/z calcd for C25H36Si2+ (M)+ 392.2356, found 392.2355. Trimethyl(5-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-3-yl)silane (5b). 5b (4b: 65.0 mg, 13935


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procedure (petroleum ether) as a white solid. mp: 94.3−101.6 °C. 1H NMR (400 MHz, CDCl3, δ ppm) 7.41 (d, J = 7.6 Hz, 1H), 7.26 (s, 2H), 7.18 (s, 2H), 7.05 (t, J = 7.2 Hz, 1H), 6.88 (d, J = 7.6 Hz, 1H), 3.48 (d, J = 11.2 Hz, 1H), 2.49 (s, 1H), 1.94 (s, 1H), 1.53 (t, J = 11.2 Hz, 1H), 1.39 (t, J = 11.6 Hz, 1H), 1.26−1.14 (m, 3H), 0.54 (d, J = 9.6 Hz, 1H), 0.31 (s, 10H), −0.48 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 148.5, 142.9, 142.8, 140.0, 134.8, 134.7, 133.2, 132.6, 131.0, 127.5, 126.4, 124.5, 55.0, 43.8, 43.2, 38.7, 38.0, 33.0, 32.8, 2.1, −0.5. HRMS (EI) m/z calcd for C25H35ClSi2+ (M)+ 426.1966, found 426.1967. Methyl 3′-(Trimethylsilyl)-2′-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-4-carboxylate (5h). 5h (31.6 mg, 35%) was prepared according to the typical procedure (petroleum ether/ethyl acetate = 30:1) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.97 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.42 (s, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.07 (t, J = 7.2 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 3.86 (s, 3H), 3.49 (d, J = 11.2 Hz, 1H), 2.50 (s, 1H), 1.91 (s, 1H), 1.53−1.47 (m, 1H), 1.39−1.33 (m, 1H), 1.23−1.20 (m, 1H), 1.18−1.13 (m, 2H), 0.45 (d, J = 10 Hz, 1H), 0.31 (s, 9H), 0.24 (d, J = 10 Hz, 1H), −0.47 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 167.1, 149.4, 148.2, 142.9, 140.2, 134.9, 134.3, 132.0, 129.8, 128.9, 128.4, 127.4, 124.5, 55.0, 52.0, 43.8, 43.1, 38.7, 37.9, 33.0, 32.7, 2.1, −0.6. HRMS (ESI) m/z calcd for C27H38O2Si2+ (M + Na)+ 473.2410, found 473.2412. (3′-Fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-3-yl)trimethylsilane (5i). 5i (56.7 mg, 69%, 1:1) was prepared according to the typical procedure (petroleum ether) as a white solid. 1H NMR (400 MHz, CDCl3, δ ppm) 7.53 (d, J = 7.2 Hz, 2H), 7.34 (q, J = 6.8 Hz, 1H), 7.25−7.21 (m, 2H), 7.18−7.13 (m, 4H), 7.08−7.00 (m, 1H), 3.60 (d, J = 11.2 Hz, 2H), 2.64 (s, 2H), 2.06 (s, 2H), 1.64 (t, J = 12.0 Hz, 2H), 1.52− 1.45 (m, 2H), 1.39−1.25 (m, 6H), 0.64 (t, J = 10.4 Hz, 2H), 0.43 (s, 20H), −0.35 (d, J = 6.4 Hz, 18H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 162.7 (d, J = 89.1 Hz) 160.3 (d, J = 88.0 Hz), 148.3 (d, J = 5.1 Hz), 146.6 (d, J = 7.3 Hz),146.5 (d, J = 6.8 Hz), 142.8 (d, J = 2.5 Hz), 140.0, 134.8, 134.5, 128.8 (d, J = 8.7 Hz), 127.8 (d, J = 8.8 Hz), 127.7 (d, J = 8.8 Hz), 125.7 (d, J = 3.1 Hz), 124.5 (d, J = 1.8 Hz), 118.8 (d, J = 21.5 Hz), 117.0 (d, J = 21.1 Hz), 113.6 (d, J = 21.2 Hz), 113.3 (d, J = 20.5 Hz), 55.1, 55.0, 43.8, 43.7, 43.3, 43.2, 38.8, 38.7, 38.0, 37.8, 33.0, 32.9, 32.8, 32.8, 2.1, −0.5, −0.6. HRMS (EI) m/z calcd for C25H35FSi2+ (M)+ 410.2261, found 410.2261. 4-(3-(Trimethylsilyl)-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)phenyl)pyridine (5j). 5j (44.9 mg, 57%) was prepared according to the typical procedure (petroleum ether/ethyl acetate = 3:1) as a yellow solid. mp: 118.2−120.0 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 8.60 (s, 1H), 8.49 (s, 1H), 7.52 (d, J = 7.0 Hz, 1H), 7.37 (s, 1H), 7.26 (s, 1H), 7.17−7.15 (m, 1H), 6.92 (d, J = 7.0 Hz, 1H), 3.57 (d, J = 11.0 Hz, 1H), 2.57 (s, 1H), 2.03 (s, 1H), 1.60− 1.58 (m, 1H), 1.49−1.44 (m, 1H), 1.33−1.27 (m, 2H), 1.21 (s, 1H), 0.60 (d, J = 9.5 Hz, 1H), 0.39 (s, 10H), −0.40 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 152.6, 149.2, 147.9, 147.6, 143.2 138.5, 135.2, 134.0, 127.0, 124.9, 124.7, 54.9, 43.8, 43.1, 38.7, 38.2, 32.9, 32.7, 2.0, −0.5. HRMS (ESI-TOF) m/z calcd for C24H36NSi2+ (M +H)+ 394.2381, found 394.2384. 2-Bromo-5-fluoro-1,1′-biphenyl (6c). 6c (125.5 mg, 50%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.62 (q, J = 5.5 Hz, 8.5 Hz 1H), 7.46−7.39 (m, 5H), 7.07 (dd, J = 3.0 Hz, 9.0 Hz 1H), 6.94 (td, J = 3.0 Hz, 8.5 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 161.7 (d, J = 245.7 Hz), 144.3 (d, J = 8.0 Hz), 140.1, 134.3 (d, J = 8.3 Hz) 129.2, 128.1, 128.0, 118.2 (d, J = 22.6 Hz), 116.8 (d, J = 3.4 Hz), 115.8 (d, J = 21.9 Hz). HRMS (ESI) m/z calcd for C12H9I+ (M+H)+ 250.9793, found 250.9791. ((1R,2S,3S,4S)-3-(2-Iodophenyl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane (7). 7 (68.9 mg, 93%) was prepared according to the literature14 (petroleum ether) as a colorless oil. 1H NMR (400 MHz, CDCl3, δ ppm) 7.77 (d, J = 7.6 Hz, 1H), 7.34 (d, J = 7.6 Hz, 1H), 7.26 (t, J = 7.2 Hz, 1H), 6.83 (t, J = 7.2 Hz, 1H), 3.24 (d, J = 10.4 Hz, 1H), 2.37 (s, 2H), 1.84 (d, J = 9.6 Hz, 1H), 1.77−1.71 (m, 1H), 1.64−1.58 (m, 1H), 1.47−1.37 (m, 4H), −0.30 (s, 9H). 13C{1H}

80%; 6b: 65,0 mg, 80%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 66.5−73.4 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.42 (d, J = 8.0 Hz, 1H), 7.39−7.27 (m, 5H), 6.87 (d, J = 1.5 Hz, 1H), 3.55 (d, J = 11.0 Hz, 1H), 2.64 (d, J = 3.0 Hz, 1H), 2.31 (s, 3H), 2.02 (d, J = 3.5 Hz, 1H), 1.64−1.58 (m, 1H), 1.48−1.44 (m, 1H), 1.36−1.34 (m, 1H), 1.31−1.29 (m, 1H), 1.26−1.21 (m, 1H), 0.54 (d, J = 10.0 Hz, 1H), 0.42 (s, 9H), 0.35 (d, J = 10.0 Hz, 1H), −0.35 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 145.5, 144.5, 142.4, 141.1, 135.5, 135.2, 133.4, 131.8, 129.8, 127.4, 126.5, 126.1, 54.6, 43.8, 43.4, 38.7, 37.8, 33.1, 32.8, 20.7, 2.1, −0.5. HRMS (EI) m/z calcd for C26H38Si2+ (M)+ 406.2512, found 406.2503. (5-Fluoro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)-[1,1′-biphenyl]-3-yl)trimethylsilane (5c). 5c (4c: 68.2 mg, 83%; 6c: 59.9 mg, 73%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 110.0−113.0 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.38−7.37 (m, 2H), 7.31 (s, 2H), 7.28− 7.26 (m, 1H), 7.20−7.19 (m, 1H), 6.74−6.71 (m, 1H), 3.53 (d, J = 11.0 Hz, 1H), 2.60 (s, 1H), 2.00 (s, 1H), 1.62−1.59 (m, 1H), 1.48− 1.43 (m, 1H), 1.33−1.28 (m, 2H), 1.22−1.21 (s, 1H), 0.53 (d, J = 9.0 Hz, 1H), 0.41 (s, 9H), 0.30 (d, J = 9.5 Hz, 1H), −0.34 (s, 9H). 13 C{1H} NMR (125 MHz, CDCl3, δ ppm) 159.6 (d, J = 246.3 Hz), 145.8 (d, J = 2.8 Hz), 144.4 (d, J = 2.7 Hz), 143.1, 143.0, 131.6, 129.6, 127.6, 127.0, 126.3, 120.8 (d, J = 7.2 Hz), 120.6 (d, J = 5.3 Hz), 54.4, 43.9, 43.4, 38.7, 37.7, 33.0, 32.8, 1.9, −0.4. HRMS (EI) m/ z calcd for C25H35FSi2+ (M)+ 410.2261, found 410.2260. (5-Chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan2-yl)-[1,1′-biphenyl]-3-yl)trimethylsilane (5d). 5d (66.6 mg, 78%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 113.0−116.7 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.44 (d, J = 2.0 Hz, 1H), 7.42−7.36 (m, 2H), 7.34−7.30 (m, 2H), 7.29−7.26 (m, 1H), 7.04 (d, J = 2.0 Hz, 1H), 3.53 (d, J = 11.0 Hz, 1H), 2.61 (d, J = 3.5 Hz, 1H), 2.02 (d, J = 3.5 Hz, 1H), 1.64− 1.57 (m, 1H), 1.49−1.43 (m, 1H), 1.34 (d, J = 11.0 Hz, 1H), 1.29− 1.26 (m, 1H), 1.24−1.20 (m, 1H), 0.54 (d, J = 10.0 Hz, 1H), 0.42 (s, 9H), 0.33 (d, J = 10.0 Hz, 1H), −0.33 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 147.1, 145.5, 143.0, 142.9, 134.0, 133.8, 131.7, 130.4, 129.6, 127.6, 127.1, 126.3, 54.6, 43.9, 43.3, 38.7, 37.8, 33.0, 32.8, 1.9, −0.4. HRMS (EI) m/z calcd for C25H35ClSi2+ (M)+ 426.1966, found 426.1967. Trimethyl(2′-methyl-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-3-yl)silane (5e). 5e (62.3 mg, 79%) was prepared according to the typical procedure (petroleum ether) as a colorless oil. 1H NMR (500 MHz, CDCl3, δ ppm) 7.49 (d, J = 6.5 Hz, 1H), 7.41 (d, J = 6.0 Hz, 1H), 7.23−7.20 (m, 2H), 7.15− 7.14 (m, 2H), 6.88 (d, J = 6.5 Hz, 1H), 3.52 (d, J = 11.0 Hz, 1H), 2.20 (s, 1H), 2.07 (s, 1H), 1.94 (s, 3H), 1.59−1.57 (m, 1H), 1.49 (d, J = 11.0 Hz, 2H), 1.23 (s, 2H), 0.80 (d, J = 9.0 Hz, 1H), 0.55 (d, J = 9.0 Hz, 1H), 0.40 (s, 9H), −0.31 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3, δ ppm) 148.3, 144.5, 142.2, 139.3, 137.1, 134.4, 129.5, 129.0, 127.0, 124.9, 124.8, 54.7, 44.1, 39.9, 38.9, 38.4, 33.0, 32.8, 20.7, 2.1, −0.1. HRMS (EI) m/z calcd for C26H38Si2+ (M)+ 406.2512, found 406.2501. (4′-Methoxy-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-3-yl)trimethylsilane (5f). 5f (4f: 68.5 mg, 81%; 6f: 68.4 mg, 81%) was prepared according to the typical procedure (petroleum ether) as a white solid. mp: 55.5−65.7 °C. 1H NMR (500 MHz, CDCl3, δ ppm) 7.48 (d, J = 6.5 Hz, 1H), 7.32−7.30 (d, J = 8.0 Hz, 1H), 7.24 (d, J = 8.5 Hz, 1H), 7.14−7.12 (m, 1H), 7.02 (d, J = 7.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 6.82 (d, J = 8.0 Hz, 1H), 3.86 (s, 3H), 3.56 (d, J = 11.0 Hz, 1H), 2.64 (s, 1H), 2.01 (s, 1H), 1.61−1.59 (m, 1H), 1.49−1.45 (m, 1H), 1.35−1.28 (m, 3H), 0.61 (d, J = 9.5 Hz, 1H), 0.43−0.40 (m, 10H), −0.38 (s, 9H). 13 C{1H} NMR (125 MHz, CDCl3, δ ppm) 158.4, 148.8, 142.5, 141.0, 136.9, 135.3, 134.3, 132.8, 130.8, 124.4, 112.5, 111.8, 55.3, 55.1, 43.8, 43.4, 38.7, 37.9, 33.1, 32.8, 2.1, −0.5. HRMS (EI) m/z calcd for C26H38OSi2+ (M)+ 422.2461, found 422.2463. (4′-Chloro-2-((1S,2S,3S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-3-yl)trimethylsilane (5g). 5g (4g: 51.3 mg, 60%; 6g: 21.3 mg, 25%) was prepared according to the typical 13936


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The Journal of Organic Chemistry NMR (100 MHz, CDCl3, δ ppm) 148.4, 139.1, 128.1, 127.5, 127.3, 105.2, 55.5, 44.0, 40.2, 38.9, 38.4, 32.3, 32.2, −0.4. HRMS (ESI) m/z calcd for C16H24ISi+ (M+H)+ 371.0686, found 371.0682. ((1R,2S,3S,4S)-3-(3-Iodo-[1,1′-biphenyl]-2-yl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane (8). 8 (85.7 mg, 96%) was prepared according to the literature14 (petroleum ether) as a colorless oil (85.7 mg, 96%). 1H NMR (400 MHz, CDCl3, δ ppm) 7.92 (d, J = 8.0 Hz, 1H), 7.33 (d, J = 11.2 Hz, 5H), 6.97 (d, J = 7.6 Hz, 1H), 6.78 (t, J = 7.6 Hz, 1H), 3.62 (d, J = 10.8 Hz, 1H), 2.47 (s, 1H), 2.09 (s, 1H), 1.82 (d, J = 10.8 Hz, 1H), 1.61−1.56 (m, 1H), 1.40−1.37 (m, 1H), 1.31−1.26 (m, 2H), 0.65 (q, J = 9.6 Hz, 2H), −0.21 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ ppm) 144.4, 143.0, 141.5, 139.8, 133.5, 131.0, 129.5, 127.3, 126.5, 126.1, 109.0, 60.0, 42.0, 40.2, 38.7, 38.3, 33.3, 32.5, 0.0. HRMS (ESI-TOF) m/z calcd for C22H28ISi+ (M+H)+ 447.0999, found 447.0996.

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(3) For selected excellent studies, see: (a) 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. (b) Li, R.; Dong, G. Direct Annulation between Aryl Iodides and Epoxides through Palladium/Norbornene Cooperative Catalysis. Angew. Chem., Int. Ed. 2018, 57, 1697−1701. (c) Shi, G.; Shao, C.; Ma, X.; Gu, Y.; Zhang, Y. Pd(II)-Catalyzed Catellani-Type Domino Reaction Utilizing Arylboronic Acids as Substrates. ACS Catal. 2018, 8, 3775−3779. (d) Sun, F.; Li, M.; He, C.; Wang, B.; Li, B.; Sui, X.; Gu, Z. Cleavage of the C(O)-S Bond of Thioesters by Palladium/ Norbornene/Copper Cooperative Catalysis: An Efficient Synthesis of 2-(Arylthio)aryl Ketones. J. Am. Chem. Soc. 2016, 138, 7456−7459. (e) Wang, J.; Zhang, L.; Dong, Z.; Dong, G. Reagent-Enabled orthoAlkoxycarbonylation of Aryl Iodides via Palladium/Norbornene Catalysis. Chem. 2016, 1, 581−591. (f) Shi, H.; Babinski, D. J.; Ritter, T. Modular C-H Functionalization Cascade of Aryl Iodides. J. Am. Chem. Soc. 2015, 137, 3775−3778. (g) Dong, Z.; Wang, J.; Ren, Z.; Dong, G. Angew. Chem., Int. Ed. 2015, 54, 12664−12668. (4) For selected excellent studies, see: (a) Casnati, A.; Gemoets, H. P. L.; Motti, E.; Ca’, N. D.; Noël, T. Homogeneous and Gas-Liquid Catellani-type Reaction Enabled by Continuous-Flow Chemistry. Chem. - Eur. J. 2018, 24, 14079−14083. (b) Chen, S.; Liu, Z.-S.; Yang, T.; Hua, Y.; Zhou, Z.; Cheng, H.-G.; Zhou, Q. The Discovery of a Palladium(II)-Initiated Borono-Catellani Reaction. Angew. Chem., Int. Ed. 2018, 57, 7161−7165. (c) Dong, Z.; Lu, G.; Wang, J.; Liu, P.; Dong, G. Modular ipso/ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis. J. Am. Chem. Soc. 2018, 140, 8551−8562. (d) Wang, J.; Li, W.; Dong, Z.; Liu, P.; Dong, G. Complementary site-selectivity in arene functionalization enabled by overcoming the ortho constraint in palladium/norbornene catalysis. Nat. Chem. 2018, 10, 866−872. (5) (a) Della Ca’, M.; Maestri, G.; Malacria, M.; Derat, E.; Catellani, M. Palladium-Catalyzed Reaction of Aryl Iodides with orthoBromoanilines and Norbornene/Norbornadiene: Unexpected Formation of Dibenzoazepine Derivatives. Angew. Chem., Int. Ed. 2011, 50, 12257−12261. (b) Zhou, H.; Chen, W.; Chen, Z. Pd/Norbornene Collaborative Catalysis on the Divergent Preparation of Heterocyclic Sulfoximine Frameworks. Org. Lett. 2018, 20, 2590−2594. (c) Zheng, H.; Zhu, Y.; Shi, Y. Palladium(0)-Catalyzed Heck Reaction/C-H Activation/Amination Sequence with Diaziridinone: A Facile Approach to Indolines. Angew. Chem., Int. Ed. 2014, 53, 11280− 11284. (d) Jafarpour, F.; Jalalimanesh, N.; Teimouri, M.; Shamsianpour, M. Palladium/norbornene chemistry: an unexpected route to methanocarbazole derivatives via three Csp3-Csp2/Csp3-N/ Csp2-N bond formations in a single synthetic sequence. Chem. Commun. 2015, 51, 225−228. (6) (a) Thansandote, P.; Hulcoop, D. G.; Langer, M.; Lautens, M. Palladium-Catalyzed Annulation of Haloanilines and Halobenzamides Using Norbornadiene as an Acetylene Synthon: A Route to Functionalized Indolines, Isoquinolinones, and Indoles. J. Org. Chem. 2009, 74, 1673−1678. (b) Casnati, A.; Fontana, M.; Coruzzi, G.; Aresta, B. M.; Corriero, N.; Maggi, R.; Maestri, G.; Motti, E.; Ca’, N. D. Enhancing Reactivity and Selectivity of Aryl Bromides: A Complementary Approach to Dibenzo[b,f]azepine Derivatives. ChemCatChem 2018, 10, 4346. (7) (a) Hao, T.; Liang, H.; Ou-Yang, Y.; Yin, C.; Zheng, X.; Yuan, M.; Li, R.; Fu, H.; Chen, H. Palladium-Catalyzed Domino Reaction for Stereoselective Synthesis of Multisubstituted Olefins: Construction of Blue Luminogens. J. Org. Chem. 2018, 83, 4441−4454. (b) Fu, W. C.; Wang, Z.; Chan, W. T. K.; Lin, Z.; Kwong, F. Y. Regioselective Synthesis of Polycyclic and Heptagon-embedded Aromatic Compounds through a Versatile p-Extension of Aryl Halides. Angew. Chem., Int. Ed. 2017, 56, 7166−7170. (c) Cheng, M.; Yan, J.; Hu, F.; Chen, H.; Hu, Y. Palladium-catalyzed cascade reactions of 3iodochromones with aryl iodides and norbornadiene leading to annulated xanthones. Chem. Sci. 2013, 4, 526−530. (d) Larraufie, M.H.; Maestri, G.; Beaume, A.; Derat, É .; Ollivier, C.; Fensterbank, L.; Courillon, C.; Lacôte, E.; Catellani, M.; Malacria, M. Exception to the

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b02282. 1 H NMR and 13C{1H} NMR spectra of new compounds 2 and 5 and X-ray single-crystal diffraction analysis for compound 5d (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Guobo Deng: 0000-0002-5470-5706 Yun Liang: 0000-0002-2550-9220 Yuan Yang: 0000-0002-9061-1758 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21572051 and 21602057), the Opening Fund of Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University (KLCBTCMR201707 and KLCBTCMR201708), and Science and Technology Planning Project of Hunan Province (2018TP1017).

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REFERENCES

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Norbornene Chemistry: Synthesis of Norbornene

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