A General Catalytic Route to Enantioenriched Isoindolinones and

Letter Cite This: Org. Lett. XXXX, XXX, XXX−XXX

pubs.acs.org/OrgLett

A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)‑PD 172938 Sumit K. Ray,†,§ Milon M. Sadhu,†,§ Rayhan G. Biswas,†,§ Rajshekhar A. Unhale,† and Vinod K. Singh*,‡ †

Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal, MP - 462 066, India Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, UP - 208 016, India

‡

Org. Lett. Downloaded from pubs.acs.org by IOWA STATE UNIV on 01/09/19. For personal use only.

S Supporting Information *

ABSTRACT: Chiral Brønsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.

O

ptically active isoindolinones are prevalent in many natural and unnatural products of immense synthetic importance with a myriad of biological activities.1 Many of these synthetic products display important pharmacological effects (Figure 1, 1a−d). For instance, (S)PD 172938 1a is a noted dopamine D4 ligand,2 and pazinaclone (DN2327) 1b is a sedative and anxiolytic drug.3 Similarly, phthalides or isobenzofuranones are five-membered benzo-fused γ-butyrolactones frequently distributed in a wide range of bioactive compounds.4 Their intriguing pharmaceutical properties are evident from observed anticonvulsant,5 antibacterial,6 anti-HIV,7 and anticancer8 activities (Figure 1, 2a−d). Over the past few years, many efforts have been directed toward the asymmetric synthesis of isoindolinones through various diastereoselective approaches mediated by a chiral auxiliary.9 Conversely, few direct catalytic enantioselective syntheses have been reported. These include Mannich-lactamization,10 aza-Michael addition,11 enantioselective aza-Wacker-type cyclization,12 condensation of 2acylbenzaldehydes and anilines through a biomimetic approach,13 and nucleophilic addition to the in situ generated ketimine obtained from 3-aryl-3-hydroxy isoindolinones.14 On the other hand, catalytic asymmetric syntheses of phthalides have been documented involving transition metal catalyzed transfer hydrogenation of ortho-keto benzonitrile and orthoketo ester,15 bioreduction of 2-acetylbenzonitrile,16 intramolecular ketone hydroacylation,17 cycloaddition,18 aldol reaction,19 addition reaction,20 redox allylation of phthalaldehydes,21 and cyclization reaction.22 Despite the presence of some efficient approaches in the literature, there is no precedence for the synthesis of these two significant classes of compounds using a common catalytic approach. © XXXX American Chemical Society

Figure 1. Selected biologically active isoindolinones and phthalides.

α-Diazoesters are an important class of nucleophiles for the formation of an asymmetric C−C bond in various strategies with the retention of diazo functionality.23 These have been Received: November 10, 2018

A

DOI: 10.1021/acs.orglett.8b03597 Org. Lett. XXXX, XXX, XXX−XXX

Letter

Organic Letters extensively used as nucleophiles in enantioselective aldol reactions of carbonyl compounds,24 enantioselective Mannichtype reactions of aldimines25 as well as ketimines,14j,26 and asymmetric allylic alkylation reactions.27 However, α-diazoesters have not been investigated in an asymmetric Mannichlactamization and aldol-lactonization reaction for the synthesis of 3-substituted isoindolinones and phthalides. To address this, we envisioned the possibility of a common catalytic route for the synthesis of isoindolinones and phthalides by exploiting the intrinsic nucleophilic character of α-diazoesters. As outlined in Scheme 1, it was envisaged that the three-component tandem

Table 1. Catalyst Screening and Selected Entries for the Optimization of Reaction Conditionsa

Scheme 1. Proposed Tandem Mannich-Lactamization and Aldol-Lactonization Reactions

reaction involving a o-formyl methyl benzoate, an amine, and diazoester produces 3-substituted isoindolinone under the influence of a chiral Brønsted acid catalyst via Mannich-type addition to the in situ generated imine followed by lactamization. Additionally, it was also hypothesized that, in the absence of the amine, o-formyl methyl benzoate should undergo aldol reaction with α-diazoesters followed by lactonization to form the phthalide derivatives. Initially, optimization of the reaction was conducted by using 1.0 equiv of 2-formyl methylbenzoate (3a) and panisidine (PMPNH2, 5a) with 1.5 equiv of ethyl diazoacetate (EDA, 4a) in the presence of 5 mol % (R)-BINOL-derived phosphoric acid (PA1) in dichloromethane at room temperature. The catalyst PA1 failed to catalyze the reaction (Table 1, entry 1). It might be due to the poor solubility of the catalyst (PA1) in dichloromethane. However, when the reaction was performed in the presence of catalyst PA2 (R = 2,4,6-iPr3C6H2) bearing bulkier substituents, the reaction worked efficiently and afforded the desired isoindolinone 6a in 78% yield and 71% enantioselectivity (Table 1, entry 2). Encouraged by this outcome, a series of chiral phosphoric acids PA3−PA8 were evaluated for the reaction. Even though the catalyst PA3 having 9-anthracenyl substituents at the 3,3′position was fairly soluble in CH2Cl2, only a trace amount of the product was detected. The catalyst PA4 bearing 9phenanthryl substituents afforded the desired product 6a in 36% yield with 50% ee. Although the precise reason for the difference in catalytic activity between PA3 and PA4 is unclear to us, the difference in their reactivity indicates that the size of the appropriate chiral pocket formed by introduction of the substituents with different steric hindrance at the 3,3′-position of the phosphoric acid is crucial. Among all the catalysts screened, PA7 (H8-TRIP) was found to be the best catalyst to afford isoindolinone 6a in 94% yield with 85% ee (Table 1, entry 7). Notably, the presence of 4 Å molecular sieves has a

entry

catalyst

solvent

t (h)

yield (%)b

ee (%)c

1 2 3 4 5 6 7 8 9d 10 11 12 13 14 15 16e 17f 18e,g

PA1 PA2 PA3 PA4 PA5 PA6 PA7 PA8 PA7 PA7 PA7 PA7 PA7 PA7 PA7 PA7 PA7 PA7

CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CHCl3 DCE toluene Et2O xylene dioxane DCE DCE DCE

24 20 48 48 48 48 20 48 24 24 20 24 24 24 36 24 36 36

NR 78 trace 36 29 trace 94 trace 82 90 96 90 82 80 90 96 92 88

− 71 ND 50 25 ND 85 ND 83 78 89 77 77 75 83 95 94 91

a

Reaction conditions: 3a (0.2 mmol), 4a (0.3 mmol), 5a (0.2 mmol), 4 Å MS (50 mg), PA (0.01 mmol), and solvent (2 mL), unless specified. bIsolated yield of 6a. cDetermined by HPLC using chiralpak ID column. dWithout MS. eReaction was conducted at 0 °C. f Reaction was conducted at −20 °C. g0.004 mmol of PA was used. ND = Not determined. NR = No reaction.

positive effect on yield as well as enantioselectivity (Table 1, entry 9). Further, the solvent effect on the enantioselectivity of the product was evaluated (Table 1, entries 10−15). Among various solvents screened, 1,2-dichloroethane (DCE) was found to be the best solvent as the enantioselectivity of 6a was slightly improved to 89% (Table 1, entry 11). For further improvement of the enantioselectivity, the reaction was carried out at 0 °C, affording the product 6a in 96% yield with 95% ee (Table 1, entry 16). Furthermore, lowering the catalyst loading and reaction temperature had an adverse effect on the enantioselectivity as well as reaction rate (Table 1, entries 17−18). Having identified the best experimental reaction conditions, the substrate scope for isoindolinone formation was explored. Initially, a number of α-diazo esters were subjected to the B


Letter

Organic Letters Scheme 2. Substrate Scope for Isoindolinones

a

Reaction was conducted in 1.5 g sclae of 3a.

partner, the desired isoindolinone 6r was not formed. This might be due to the sluggish formation of the aldimine derived from sterically demanding o-anisidine. Furthermore, an aliphatic amine such as benzylamine was examined for the tandem reaction, providing corresponding product 6z in 45% yield with 40% enantioselectivity (Scheme 2). To demonstrate the practical usefulness of the tandem Mannich-lactamization process, a gram-scale reaction of methyl 2-formylbenzoate 3a (9.15 mmol, 1.5 g), 5a (9.15 mmol), and ethyl diazoacetate (13.72 mmol) was conducted under optimized conditions, affording 6a in 92% yield with 95% ee. Having successfully synthesized a broad array of isoindolinones, we next turned our attention toward the synthesis of biologically interesting phthalides using the same catalytic system. To this end, we initiated our investigation by the reaction of methyl 2-formylbenzoate (3a) and EDA (4a) under the previously identified optimized reaction conditions. 3Substituted phthalide 7a was afforded in 78% yield with 70% ee via tandem aldol-lactonization reaction. Further optimization studies were performed to improve the enantioselectivity (see Supporting Information (SI) for more details). Extensive optimization studies revealed that 5 mol % of PA7 in dichloromethane at −20 °C was found to promote the aldollactonization reaction most effectively considering yields and enantioselectivities.

reaction under optimized conditions. A variety of isoindolinones having α-diazo ester (6a−g) were obtained in good yields (up to 96%) with excellent enantioselectivities (up to 96% ee). Notably, bulky diazo ester 4c also partcipated in the reaction, affording 6c in 90% yield with 90% ee. Among differently substituted benzyl diazoacetates (4d−g) screened, fluorine-containing benzyl diazoacetate took relatively less time for completion of the reaction and furnished the isoindolinone 6g in 95% yield with 96% ee. Next, a wide range of sterically and electronically different o-formyl methyl benzoates were tested in the three-component reaction. oFormyl methyl benzoates having diverse substituents on the aromatic ring were reacted smoothly and yielded corresponding isoindolinones 6h−p in excellent yields (up to 96%) with consistently excellent enantioselectivities. Methyl 2-formyl-6methylbenzoate required a longer time for completion of the reaction, furnishing the product 6l in 80% yield with 96% ee. A series of 4-substituted o-formyl methylbenzoates furnished isoindolinones 6n−p in 99% enantioselectivities. Subsequently, to establish the generality of the tandem reaction, a variety of amines were employed under optimized reaction conditions. Aromatic amines reacted efficiently and furnished the desired isoindolinones in 85−90% yields with 90−96% ee. It is noteworthy to mention that the steric factor has a crucial role in the product formation (6r, 6s, and 6a). Surprisingly, when o-anisidine was introduced as an amine C


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Organic Letters

(up to 85% ee). Significantly, the electronic properties of the substituent attached to the aromatic ring of the o-formyl methyl benzoates had negligible effect on the optical yields of the products. Phthalide 7l was crystallized from the mixture of diethyl ether/pentane solvent. The absolute stereochemistry of compound 7l was unambiguously determined by X-ray crystal structure analysis (CCDC 1872475). The absolute configurations of the other phthalides within series 7 were assigned by analogy. To gain some insight into the role of the ester moiety in the substrates (3), control experiments were conducted. Reaction of 4a with benzaldehyde (3a′) under optimized conditions did not yield either the Mannich-product or the aldol-product (see SI for details). This outcome indicates that the ester moiety in the substrate plays a crucial role in the product formation. To rationalize the observed stereochemical outcome, a plausible transition state model was proposed (Figure 2).25a,e,28

Next, the scope of the phthalide formation was explored with a wide variety of α-diazo esters and 2-formyl methyl benzoates (Scheme 3). Initially, an array of α-diazo esters with Scheme 3. Substrate Scope for Phthalide

Figure 2. Plausible transition state model.

Chiral phosphoric acid acts as a bifunctional catalyst having both Brønsted acid and Brønsted basic sites. Initially, imine/ aldehyde and an ester moiety were activated by an acidic proton through hydrogen bonding and then nucleophilic αdiazoester attacked the Si- face of the imine/aldehyde. Subsequently, α-diazoester was deprotonated by the phosphoryl oxygen (Brønsted basic site). Finally, lactamization/ lactonization provides the desired product. To demonstrate the synthetic utility of the protocol, the enantioenriched isoindolinone 6a was transformed into the corresponding hydrazone derivative 8 in 87% yield with 93% ee by NaBH4 reduction. The treatment of 6a with Adams’ catalyst under a hydrogen atmosphere furnished 8 and compound 9 (by complete removal of diazo group) in 68% and 15% yields respectively with the retention of enantioselectivities. In addition, the phthalide 7q was successfully reduced to corresponding hydrazone 10 in 68% yield using a H2/PtO2 catalytic system with erosion in enantiopurity (71% ee).29 Subsequently, hydrazone 10 was efficiently converted into α-keto ester 11 in 70% yield and with retention of enantioselectivity (Scheme 4). The title reaction was eventually applied in a concise synthesis of (S)-PD 172938 (Scheme 5). The synthesis includes removal of the diazo moiety from enantioenriched isoindolinone 6a to provide compound 9 in 70% yield and subsequent removal of the PMP group by using cerium(IV)

a

ee after recrystallization in ether−pentane mixture.

delicate functionalities were tested. Phthalides 7a−g were obtained in good to excellent yields (up to 90%) and enantioselectivities (up to 85% ee). Among various diazoacetates screened, benzyl diazo acetate was best to afford the corresponding phthalide 7d with 85% ee. Then, we investigated the scope of the aldol-lactonization tandem reaction by conducting the reaction of benzyl diazo ester with a series of methyl 2-formylbenzoates. Interestingly, enantioenriched phthalides containing diazo ester 7h−p were afforded in good yields (up to 85%) and enantioselectivities D


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Organic Letters

Then, 13 was converted to 1a using a procedure described in literature.11d,30 In summary, we have demonstrated a Brønsted acid catalyzed enantioselective synthesis of isoindolinones and phthalides via tandem Mannich-lactamization and aldollactonization reactions, respectively, from readily available precursors. The strategy provides facile access to a variety of Nand O-heterocycles in excellent yields (up to 96%) and enantioselectivities (up to 99% ee). The catalytic system is amenable to gram-scale synthesis of isoindolinones. The synthetic potential of this methodology has also been demonstrated by exploiting the reactivity of diazo functionality in the product. Additionally, a concise total synthesis of (S)PD 172938 has been accomplished by using this protocol.

Scheme 4. Synthetic Transformations

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.8b03597. Experimental details and analytical data (NMR, HPLC, and ESI-HRMS) (PDF) Accession Codes

CCDC 1872475 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Scheme 5. Synthesis of (S)-PD 172938

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Milon M. Sadhu: 0000-0001-5273-1997 Vinod K. Singh: 0000-0003-0928-5543 Author Contributions §

S.K.R., MM.S., and R.G.B. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS V.K.S. thanks the DST India, for the J. C. Bose fellowship. S.K.R. thanks DST for the INSPIRE Faculty award (DST/ INSPIRE/04/2016001704). M.M.S. thanks DST for an Inspire fellowship. We are thankful to Dr. Atanu Dey, TIFR Hyderabad, for assistance with X-ray crystallography.

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REFERENCES

(1) (a) Di Mola, A.; Palombi, L.; Massa, A. Curr. Org. Chem. 2012, 16, 2302. (b) Speck, K.; Magauer, T. Beilstein J. Org. Chem. 2013, 9, 2048. (2) Belliotti, T. R.; Brink, W. A.; Kesten, S. R.; Rubin, J. R.; Wustrow, D. J.; Zoski, K. T.; Whetzel, S. Z.; Corbin, A. E.; Pugsley, T. A.; Heffner, T. G.; Wise, L. D. Bioorg. Med. Chem. Lett. 1998, 8, 1499. (3) Hussein, Z.; Mulford, D. J.; Bopp, B. A.; Granneman, G. R. Br. J. Clin. Pharmacol. 1993, 36, 357. (4) (a) Lin, G.; Chan, S. S.-K.; Chung, H.-S.; Li, S.-L. In Studies in Natural Products Chemistry: Bioactive Natural Products, Vol. 32 (Part L); Atta-ur-Rahman, Ed.; Elsevier: Amsterdam, 2005; p 611.

ammonium nitrate (CAN) to furnish intermediate 12 in 90% yield with retention of enantioselectivity (95% ee). The latter was then reduced with LiBH4 to afford alcohol 13 in 85% yield. E


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Organic Letters (b) Karmakar, R.; Pahari, P.; Mal, D. Chem. Rev. 2014, 114, 6213. (c) Fan, Y. C.; Kwon, O. Org. Lett. 2012, 14, 3264. (d) Liu, J.; Miotto, R. J.; Segard, J.; Erb, A. M.; Aponick, A. Org. Lett. 2018, 20, 3034. (e) Zhong, F.; Luo, J.; Chen, G.-Y.; Dou, X.; Lu, Y. J. Am. Chem. Soc. 2012, 134, 10222. (f) Fujioka, M.; Morimoto, T.; Tsumagari, T.; Tanimoto, H.; Nishiyama, Y.; Kakiuchi, K. J. Org. Chem. 2012, 77, 2911. (5) Yu, S.; You, S.; Chen, H. Yaoxue Xuebao 1984, 101, 486. (6) Holler, U.; Gloer, J. B.; Wicklow, D. T. J. Nat. Prod. 2002, 65, 876. (7) Yoganathan, K.; Rossant, C.; Ng, S.; Huang, S. Y.; Butler, M. S.; Buss, A. D. J. Nat. Prod. 2003, 66, 1116. (8) Palermo, J. A.; Rodriguez Brasco, M. F.; Spagnuolo, C.; Seldes, A. M. J. Org. Chem. 2000, 65, 4482. (9) (a) Grigg, R.; Dorrity, M. J. R.; Malone, J. F.; Mongkolaussavaratana, T.; Norbert, W. D. J. A.; Sridharan, V. Tetrahedron Lett. 1990, 31, 3075. (b) McAlonan, H.; Murphy, J. P.; Nieuwenhuyzen, M.; Reynolds, K.; Sarma, P. K. S.; Stevenson, P. J.; Thompson, N. J. Chem. Soc., Perkin Trans. 1 2002, 69. (c) Enders, D.; Braig, V.; Raabe, G. Can. J. Chem. 2001, 79, 1528. (d) Adachi, S.; Onozuka, M.; Yoshida, Y.; Ide, M.; Saikawa, Y.; Nakata, M. Org. Lett. 2014, 16, 358. (e) Bahajaj, A. A.; Vernon, J. M.; Wilson, G. D. Tetrahedron 2004, 60, 1247. (f) Chen, M.-D.; Zhou, X.; He, M.-Z.; Ruan, Y.-P.; Huang, P.-Q. Tetrahedron 2004, 60, 1651. (g) PérardViret, J.; Prangé, T.; Tomas, A.; Royer, J. Tetrahedron 2002, 58, 5103. (h) Comins, D. L.; Schilling, S.; Zhang, Y. Org. Lett. 2005, 7, 95 and references therein . (10) (a) Wang, Z.-Q.; Feng, C.-G.; Xu, M.-H.; Lin, G.-Q. J. Am. Chem. Soc. 2007, 129, 5336. (b) Guo, S.; Xie, Y.; Hu, X.; Xia, C.; Huang, H. Angew. Chem., Int. Ed. 2010, 49, 2728. (c) Bisai, V.; Suneja, A.; Singh, V. K. Angew. Chem., Int. Ed. 2014, 53, 10737. (d) Tiso, S.; Massa, A. J. Heterocycl. Chem. 2015, 52, 1570. (e) Bisai, V.; Unhale, R. A.; Suneja, A.; Dhanasekaran, S.; Singh, V. K. Org. Lett. 2015, 17, 2102. (f) Zhang, Y.; Ao, Y.-F.; Huang, Z.-T.; Wang, D.-X.; Wang, M.X.; Zhu, J. Angew. Chem., Int. Ed. 2016, 55, 5282. (g) Suneja, A.; Bisai, V.; Singh, V. K. J. Org. Chem. 2016, 81, 4779. (h) Jiang, T.; Chen, W.W.; Xu, M.-H. Org. Lett. 2017, 19, 2138. (i) Unhale, R. A.; Molleti, N.; Rana, N. K.; Dhanasekaran, S.; Bhandary, S.; Singh, V. K. Tetrahedron Lett. 2017, 58, 145. (j) He, Y.; Cheng, C.; Chen, B.; Duan, K.; Zhuang, Y.; Yuan, B.; Zhang, M.; Zhou, Y.; Zhou, Z.; Su, Y.J.; Cao, R.; Qiu, L. Org. Lett. 2014, 16, 6366. (11) (a) More, V.; Rohlmann, R.; Mancheno, O. G.; Petronzi, C.; Palombi, L.; Rosa, A. D.; Mola, A. D.; Massa, A. RSC Adv. 2012, 2, 3592. (b) Tiso, S.; Palombi, L.; Vignes, C.; Di Mola, A.; Massa, A. RSC Adv. 2013, 3, 19380. (c) Sallio, R.; Lebrun, S.; Schifano-Faux, N.; Goossens, J.-F.; Agbossou-Niedercorn, F.; Deniau, E.; Michon, C. Synlett 2013, 24, 1785. (d) Di Mola, A.; Tiffner, M.; Scorzelli, F.; Palombi, L.; Filosa, R.; De Caprariis, P.; Waser, M.; Massa, A. Beilstein J. Org. Chem. 2015, 11, 2591. (e) Lebrun, S.; Sallio, R.; Dubois, M.; Agbossou-Niedercorn, F.; Deniau, E.; Michon, C. Eur. J. Org. Chem. 2015, 2015, 1995. (f) Enders, D.; Braig, V.; Raabe, G. Can. J. Chem. 2001, 79, 1528. (12) Yang, G.; Shen, C.; Zhang, W. Angew. Chem., Int. Ed. 2012, 51, 9141. (13) Min, C.; Lin, Y.; Seidel, D. Angew. Chem., Int. Ed. 2017, 56, 15353. (14) (a) Yu, X.; Wang, Y.; Wu, G.; Song, H.; Zhou, Z.; Tang, C. Eur. J. Org. Chem. 2011, 2011, 3060. (b) Nishimura, T.; Noishiki, A.; Ebe, Y.; Hayashi, T. Angew. Chem., Int. Ed. 2013, 52, 1777. (c) Chen, M.W.; Chen, Q.-A.; Duan, Y.; Ye, Z.-S.; Zhou, Y.-G. Chem. Commun. 2012, 48, 1698. (d) Zhou, J.-Q.; Sheng, W.-J.; Jia, J.-H.; Ye, Q.; Gao, J.-R.; Jia, Y.-X. Tetrahedron Lett. 2013, 54, 3082. (e) Suć, J.; Dokli, I.; Gredičak, M. Chem. Commun. 2016, 52, 2071. (f) Suneja, A.; Unhale, R. A.; Singh, V. K. Org. Lett. 2017, 19, 476. (g) Scorzelli, F.; Di Mola, A.; De Piano, F.; Tedesco, C.; Palombi, L.; Filosa, R.; Waser, M.; Massa, A. Tetrahedron 2017, 73, 819. (h) Ge, C.; Liang, R.-X.; Liu, R.R.; Xiang, B.; Jia, Y.-X. Tetrahedron Lett. 2017, 58, 142. (i) Glavač, D.; Zheng, C.; Dokli, I.; You, S.-L.; Gredičak, M. J. Org. Chem. 2017, 82, 8752. (j) Unhale, R. A.; Sadhu, M. M.; Ray, S. K.; Biswas, R. G.;

Singh, V. K. Chem. Commun. 2018, 54, 3516. (k) Kang, Z.; Zhang, D.; Shou, J.; Hu, W. Org. Lett. 2018, 20, 983. (l) Zhang, L.; Wu, B.; Chen, Z.; Hu, J.; Zeng, X.; Zhong, G. Chem. Commun. 2018, 54, 9230. (15) (a) Kitamura, M.; Ohkuma, T.; Inoue, S.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.; Ohta, T.; Takaya, H.; Noyori, R. J. Am. Chem. Soc. 1988, 110, 629. (b) Ohkuma, T.; Kitamura, M.; Noyori, R. Tetrahedron Lett. 1990, 31, 5509. (c) Everaere, K.; Scheffler, J.-L.; Mortreux, A.; Carpentier, J.-F. Tetrahedron Lett. 2001, 42, 1899. (d) Zhang, B.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2009, 11, 4712. (e) Lu, B.; Zhao, M.; Ding, G.; Xie, X.; Jiang, L.; Ratovelomanana-Vidal, V.; Zhang, Z. ChemCatChem 2017, 9, 3989. (16) Mangas-Sánchez, J.; Busto, E.; Gotor-Fernández, V.; Gotor, V. Org. Lett. 2012, 14, 1444. (17) (a) Phan, D. H. T.; Kim, B.; Dong, V. M. J. Am. Chem. Soc. 2009, 131, 15608. (b) Yang, J.; Yoshikai, N. J. Am. Chem. Soc. 2014, 136, 16748. (c) Willis, M. C. Angew. Chem., Int. Ed. 2010, 49, 6026. (18) (a) Tanaka, K.; Osaka, T.; Noguchi, K.; Hirano, M. Org. Lett. 2007, 9, 1307. (b) Tanaka, K.; Nishida, G.; Wada, A.; Noguchi, K. Angew. Chem., Int. Ed. 2004, 43, 6510. (19) Zhang, H.; Zhang, S.; Liu, L.; Luo, G.; Duan, W.; Wang, W. J. Org. Chem. 2010, 75, 368. (20) (a) Mirabdolbaghi, R.; Dudding, T. Tetrahedron 2013, 69, 3287. (b) Yohda, M.; Yamamoto, Y. Org. Biomol. Chem. 2015, 13, 10874. (c) Xing, C.-H.; Liao, Y.-X.; He, P.; Hu, Q.-S. Chem. Commun. 2010, 46, 3010. (21) Cabrera, J. M.; Tauber, J.; Krische, M. Angew. Chem., Int. Ed. 2018, 57, 1390. (22) (a) Chang, H. T.; Jeganmohan, M.; Cheng, C. H. Chem. - Eur. J. 2007, 13, 4356. (b) Youn, S. W.; Song, H. S.; Park, J. H. Org. Lett. 2014, 16, 1028. (c) Yamamoto, Y.; Ishii, J.-i.; Nishiyama, H.; Itoh, K. J. Am. Chem. Soc. 2005, 127, 9625. (23) (a) Zhang, Y.; Wang, J. Tetrahedron 2008, 64, 6577. (b) Zhang, Y.; Wang, J. Chem. Commun. 2009, 0, 5350. (c) Chen, J.; Wen, X.; Wang, Y.; Du, F.; Cai, L.; Peng, Y. Org. Lett. 2016, 18, 4336. (d) Wen, X.; Chen, J.; Peng, Y. Adv. Synth. Catal. 2014, 356, 3794. (24) (a) Yao, W.; Wang, J. Org. Lett. 2003, 5, 1527. (b) Wang, F.; Liu, X.; Zhang, Y.; Lin, L.; Feng, X. Chem. Commun. 2009, 0, 7297. (c) Benfatti, F.; Yilmaz, S.; Cozzi, P. G. Adv. Synth. Catal. 2009, 351, 1763. (d) Trost, B. M.; Malhotra, S.; Fried, B. A. J. Am. Chem. Soc. 2009, 131, 1674. (e) Trost, B. M.; Malhotra, S.; Koschker, P.; Ellerbrock, P. J. Am. Chem. Soc. 2012, 134, 2075. (f) Trost, B. M.; Malhotra, S.; Ellerbrock, P. Org. Lett. 2013, 15, 440. (g) Wang, W.; Shen, K.; Hu, X.; Wang, J.; Liu, X.; Feng, X. Synlett 2009, 2009, 1655. (25) (a) Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc. 2005, 127, 9360. (b) Hashimoto, T.; Maruoka, K. J. Am. Chem. Soc. 2007, 129, 10054. (c) Hashimoto, T.; Kimura, H.; Kawamata, Y.; Maruoka, K. Nat. Chem. 2011, 3, 642. (d) Hashimoto, T.; Kimura, H.; Nakatsu, H.; Maruoka, K. J. Org. Chem. 2011, 76, 6030. (e) Zhang, H.; Wen, X.; Gan, L.; Peng, Y. Org. Lett. 2012, 14, 2126. (f) Bew, S. P.; Carrington, R.; Hughes, D. L.; Liddle, J.; Pesce, P. Adv. Synth. Catal. 2009, 351, 2579. (g) Bew, S. P.; Liddle, J.; Hughes, D. L.; Pesce, P.; Thurston, S. M. Angew. Chem., Int. Ed. 2017, 56, 5322. (h) Hashimoto, T.; Maruoka, K. Synthesis 2008, 2008, 3703. (i) Jiang, N.; Qu, Z.; Wang, J. Org. Lett. 2001, 3, 2989. (26) Zhou, M.; Su, Q.; Addepalli, Y.; He, Y.; Wang, Z. Org. Biomol. Chem. 2018, 16, 2923. (27) Mao, H.; Lin, A.; Shi, Y.; Mao, Z.; Zhu, X.; Li, W.; Hu, H.; Cheng, Y.; Zhu, C. Angew. Chem., Int. Ed. 2013, 52, 6288. (28) Parmar, D.; Sugiono, E.; Raja, S.; Rueping, M. Chem. Rev. 2014, 114, 9047. (29) The phthalide 7p was successfully reduced to corresponding hydrazone 10 in 80% yield using NaBH4. Unfortunately the product was found to be racemic. (30) By comparing the optical rotation of 1a with the literature report, we determined the absolute configuration of the product to be (S).

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