Cobalt-Catalyzed Enantioselective and Chemodivergent Addition of

May 22, 2019 - We report herein cobalt-catalyzed enantioselective and chemodivergent reactions between a cyclopropanol and an oxabicyclic alkene via a...
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Letter Cite This: ACS Catal. 2019, 9, 5638−5644

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Cobalt-Catalyzed Enantioselective and Chemodivergent Addition of Cyclopropanols to Oxabicyclic Alkenes Junfeng Yang,*,† Yoshiya Sekiguchi, and Naohiko Yoshikai* Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore

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S Supporting Information *

ABSTRACT: We report herein cobalt-catalyzed enantioselective and chemodivergent reactions between a cyclopropanol and an oxabicyclic alkene via a cobalt homoenolate, which afford either an alkylative ringopening product or a hydroalkylation product, with the counterion of the cobalt catalyst being a major chemoselectivity-controlling factor. A catalyst generated from cobalt(II) chloride and a chiral diphosphine promotes alkylative ring opening to afford 1,2-dihydronaphthalen-1-ol derivatives in good yields with high enantioselectivity. By contrast, a catalyst generated from cobalt(II) acetate and the same diphosphine ligand, with the assistance of methanol, selectively affords hydroalkylation products with retention of the bicyclic structure at a comparable level of enantioselectivity. KEYWORDS: cobalt catalysis, asymmetric catalysis, cyclopropanes, desymmetrization, homoenolate

T

source, promoted racemic hydroallylation (Scheme 1c).4k Catalyst-controlled chemodivergence was also achieved in Fe-catalyzed arylation with arylzinc reagents by Nakamura10 and Pd-catalyzed alkynylation with terminal alkynes by Hou,11 albeit using achiral catalysts. Herein, we report on cobalt-catalyzed enantioselective and chemodivergent reactions between a cyclopropanol and an oxabicyclic alkene via a homoenolate, which afford a ringopening alkylation product or a hydroalkylation product in good yield as well as high chemo- and enantioselectivities (Scheme 1d). Unlike the aforementioned examples of chemodivergence, the chemoselectivity is controlled primarily by the counterion of the cobalt(II) precatalyst rather than the supporting ligand. The catalyst generated from CoCl2 and a chiral diphosphine promotes alkylative ring opening with high enantioselectivity, while the catalyst generated from Co(OAc)2 and the same diphosphine promotes hydroalkylation with retention of the bicyclic core at a comparable level of enantioselectivity. Besides being new examples of catalytic desymmetrization of oxabicyclic alkenes, the reactions represent a notable addition to the transition-metal-catalyzed tranformation of cyclopropanols12,13 as well as to the enantioselective C−C bond formation using earth-abundant cobalt catalysts.14,15 In pursuit of our continuing interest in cobalt-catalyzed C− C bond formation,16,17 we recently reported cobalt-catalyzed divergent coupling reactions between a cyclopropanol and an

he transition-metal-catalyzed enantioselective addition of carbon and heteroatom nucleophiles to meso-heterobicyclic alkenes has offered powerful means to synthesize densely functionalized chiral cyclic compounds.1 In their seminal work on the Pd-catalyzed reaction of oxabicyclic alkenes with dialkylzinc,2 the Lautens group set the stage for further development of desymmetrization using various hard carbon nucleophiles such as organometallic reagents and terminal alkynes leading to ring-opening3−8 or addition4c,d,k,9 products, and they also put forward the commonly accepted mechanistic framework for the product divergence (Scheme 1a). Thus, the reaction typically proceeds via syn-addition of an organotransition-metal species across the CC bond to form a carbometalation intermediate A, which then undergoes βheteroatom elimination to afford the ring-opening product. Alternatively, the intermediate A may undergo protonolysis or transmetalation to end up in the addition product without ring opening. The chemoselectivity between ring opening and addition generally depends on various factors including the nucleophile, the alkene, and the reaction conditions. As such, catalytic systems that allow for divergent access to both the products from the same nucleophile/alkene combination have been relatively sparse. Lautens reported Rh-catalyzed enantioselective reaction between an arylboronic acid and a diazabicyclic alkene, which results in ring-opening arylation or hydroarylation depending on the electronic nature of the arylboronic acid and the chiral diphosphine ligand (Scheme 1).4c,d Zhao reported Co-catalyzed reaction between allyltrifluoroborate and an oxabicyclic alkene, where a chiral diphosphine-ligated catalyst promoted asymmetric ring opening while a ligand-free catalyst, in the presence of a proton © 2019 American Chemical Society

Received: February 14, 2019 Revised: May 16, 2019 Published: May 22, 2019 5638

DOI: 10.1021/acscatal.9b00655 ACS Catal. 2019, 9, 5638−5644

Letter

ACS Catalysis Table 1. Effect of Reaction Conditionsa

Scheme 1. Transition Metal-Catalyzed Reactions between Hard Carbon Nucleophiles and Heterobicyclic Alkenes

yield (%)b entry

CoX2

ligand

temp (°C)

3a

4a

erc

1 2 3 4 5 6 7 8 9 10 11 12e 13g

CoCl2 CoBr2 CoI2 Co(OAc)2 CoCl2 CoCl2 CoCl2 CoCl2 Co(OAc)2 Co(OAc)2 Co(OAc)2 Co(OAc)2 Co(OAc)2

dppp dppp dppp dppp prophos chiraphos bdpp bdpp prophos chiraphos bdpp bdpp bdpp

25 25 25 25 60 60 60 80 60 60 60 80 80

55 42 47 12 63 61 77 87 15 25 16 8 4

11 9 11 66 4 2 5 7 63 38 37d 70f 81h

81:19 82:18 96:4 96:4 79:21 82:18 94:6 94:6 94:6

a

The reaction was performed using 0.12 mmol (for achiral ligands) or 0.15 mmol (for chiral ligands) of 1a and 0.1 mmol of 2a (0.3 M) for 12−20 h. bDetermined by GC using mesitylene as an internal standard. cEnantiomeric ratio of the major product determined by HPLC. d5a (25%) was formed. eMeOH (2 equiv) was added. f5a (14%) was formed. gMeOH (10 equiv) was added. h5a (4%) was formed.

alkyne, which afford either a β-alkenyl ketone or a cyclopentenol derivative via cobalt homoenolate.18 The cobalt homoenolate chemistry has been further extended to regioand diastereoselective formal [3 + 2] cycloaddition between a cyclopropanol and an allene.19 Prompted by these studies and the precedents on cobalt-catalyzed nucleophile addition to oxabicyclic alkenes,3d,4k,9a we initiated the present study with exploration of the reaction between 1-phenylcyclopropanol (1a, 1.2 equiv) and 7-oxabenzonorbornadiene (2a) in the presence of cobalt salt (10 mol %), diphosphine ligand (10 mol %), and DABCO (1.5 equiv) in DMSO (Table 1). Upon screening of achiral ligands (see Table S1 for detail), a catalyst generated from CoCl2 and dppp was found to promote the reaction at 25 °C to afford the ring-opening product 3a in 55% yield, accompanied by the hydroalkylation product 4a in 11% yield (entry 1). Comparable results were obtained using CoBr2 or CoI2 instead of CoCl2 (entries 2 and 3). Interestingly, the chemoselectivity was reversed using Co(OAc)2, affording 4a as the major product (66%) along with 3a in 12% yield (entry 4). Encouraged by these results, we next explored chiral diphosphine ligands (see Table S2 for detail). With CoCl2 as the precatalyst, chiral diphosphines such as prophos, chiraphos, and bdpp promoted the reaction at 60 °C to afford 3a as the major product with er of 81:19 to 96:4 (entries 5−7). Using

bdpp as the optimal ligand, the yield of 3a was improved at 80 °C without compromising the enantioselectivity (96:4 er, entry 8). A change of the precatalyst to Co(OAc)2 again resulted in moderate but distinct reversal of chemoselectivity (entries 9− 11), where ers of 4a were comparable to that of 3a in entries 5−7. We noted that the Co(OAc)2/bdpp-catalyzed reaction afforded another byproduct assigned as cyclopentanol derivative 5a in 25% yield (entry 11), which could be formed via cyclization of the carbometalation intermediate (vide infra). The addition of MeOH to this reaction significantly suppressed 3a and 5a without affecting the enantioselectivity of 4a (entries 12 and 13). Using 10 equiv of MeOH, 4a was obtained in 81% yield with 94:6 er (entry 13). Note that the effort to obtain 5a as the major product, for example, by changing the solvent, has been unsuccessful (see Table S3). The effect of DABCO deserves comments. Interestingly, other nitrogen bases such as iPr2NEt, Et3N, pyridine, and 2,6-lutidine almost completely shut down the activity of the CoCl2-based catalyst but promoted the hydroalkylation using Co(OAc)2 with comparable efficiency as DABCO (Table S4). Note also that, unlike the cobalt-catalyzed cyclopropanol/alkyne coupling,18 the present reactions did not require a reductant such as Zn, as was also the case with our recent work on the cyclopropanol/allene coupling.19 5639

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ACS Catalysis

such as those derived from electron-deficient aryl-substituted cyclopropanols, were obtained as equilibrium mixture of the ketoalcohol 3 and its hemiketal isomer. The er values of these and some other products were determined upon transformation to the corresponding silyl ethers (see the SI). Note that 1,2-disubstituted cyclopropanols such as 1,1a,2,3tetrahydro-7bH-cyclopropa[a]naphthalen-7b-ol and 2-methyl1-phenylcyclopropanol failed to undergo either alkylative ring opening or hydroalkylation, regardless of the use of chiral or achiral catalysts. A series of substituted 7-oxabenzonorbornadienes were amenable to the reaction with 1a to afford the corresponding products 3s−3w in moderate to good yields with 93:7−97:3 er. The reaction of less-strained 7oxanorbornene derivative was rather sluggish, and only a trace amount of the desired product 3x was observed by GCMS analysis. Note that attempts to promote this reaction by the addition of a Lewis acid such as Zn(OTf)2, In(OTf)3, and Ti(OiPr)4, aiming at acceleration of the C−O bond cleavage, were in vain. Likewise, 7-azabenzonorbornadiene bearing N-Boc substituent reacted sluggishly, and afforded only a trace amount of the product 3y. These unsuccessful reactions are in sharp contrast to the efficient hydroalkylation of the same substrates (vide infra). Scheme 3 shows the scope of the Co(OAc)2/bdpp-catalyzed hydroalkylation. As was the case with the alkylative ring opening, a variety of 1-arylcyclopropanols participated in the reaction with 2a to afford the desired products 4a−4p in moderate to good yields with ers ranging from 93:7 to 96:4, except that 1-(1-naphthyl)cyclopropanol reacted rather sluggishly. The racemic product of this cyclopropanol, 4o, was obtained in a moderate yield using the achiral Co(OAc)2/dppp catalyst. Benzyl- and phenylethyl-substituted cyclopropanols underwent the hydroalkylation to afford the desired products 4q and 4r, respectively, albeit in somewhat lower yields (64− 65%) with 92:8−93:7 er. The reaction of 1a with various 7oxabenzonorbornadienes proceeded smoothly, affording the corresponding products 4s−4w in good yields with 93:7−95:5 er. It is also notable that, unlike the alkylative ring opening, the hydroalkylation of oxanorbornene and azabenzonorbornadiene derivatives successfully afforded the desired adducts 4x and 4y, respectively, in good yields and enantioselectivities. X-ray crystallographic analysis of 4a determined its absolute configuration as (1R,2R,4S),20 and the same sense of stereochemistry was assumed for the rest of the hydroalkylation products as well as for the alkylative ring-opening products. To gain some insight into the counterion-dependent chemoselectivity between the ring opening and the hydroalkylation, we performed a series of control experiments (Table 2; see Table S5 for full results). The addition of an acetate salt (20 mol %) such as NaOAc, KOAc, CsOAc, or [Bu4N]OAc to the CoCl2/dppp-catalyzed reaction between 1a and 2a resulted in reversal of the chemoselectivity, affording the hydroalkylation product 4a as the major product along with minor amounts of 3a and 5a (entry 1 vs entries 2−5). Other carboxylate salts such as NaOBz and CsOPiv also caused a chemoselectivity switch (entries 6 and 7). Cs2CO3 did not show such drastic influence (entry 8), while we observed that a large portion of the carbonate salt remained undissolved. The addition of a carboxylic acid completely shut down the catalytic activity (entry 9). Carboxylate salts were also found to switch the chemoselectivity of CoBr2- and CoI2-based catalysts from ring-opening to hydroalkylation (entries 10−13). In

With the optimized conditions in hand, we explored the scope of the present alkylative ring-opening and hydroalkylation reactions. The CoCl2/bdpp-catalyzed reactions between cyclopropanols and bicyclic alkenes are summarized in Scheme 2. A series of 1-arylcyclopropanols participated in Scheme 2. Scope of Enantioselective Alkylative Ring Openinga

a

The reaction was performed on a 0.3 mmol scale. bThe product as an equilibrium mixture with its hemiketal isomer (ratio = 93:7 to 33:67). The er was determined for the corresponding TBS ether (see the Supporting Information for details). cThe enantioselectivity was determined for the corresponding TBS ether.

the alkylative ring opening of 2a to afford the corresponding products 3a−3p in good yields (62−99%) and enantioselectivities (94:6−97:3 er), with tolerance to substituents such as halogen (F, Cl, Br), methoxy, and trifluoromethyl groups. Sterically hindered ortho-methoxyphenyl and 1-naphthyl groups as well as 3-thienyl group could also be tolerated (see the products 3n−3p). The reactions of benzyl- and phenylethyl-substituted cyclopropanols also afforded the desired products 3q and 3r, respectively, in reasonable yields and good er of 96:4. It should be noted that some of the products, 5640

DOI: 10.1021/acscatal.9b00655 ACS Catal. 2019, 9, 5638−5644

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ACS Catalysis Scheme 3. Scope of Enantioselective Hydroalkylationa

Table 2. Effect of Additives on Chemodivergencea

yield (%)b entry

CoX2

additive

3a

4a

5a

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

CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoBr2 CoBr2 CoI2 CoI2 Co(OAc)2 Co(OAc)2 Co(OAc)2 Co(OPiv)2 CoCl2 CoBr2 CoI2 Co(OAc)2

none NaOAc (20 mol %) KOAc (20 mol %) CsOAc (20 mol %) [Bu4N]OAc (20 mol %) NaOBz (20 mol %) CsOPiv (20 mol %) Cs2CO3 (20 mol %) AcOH (20 mol %) none NaOAc (20 mol %) none NaOAc (20 mol %) none NaCl (20 mol %) [Bu4N]Cl (20 mol %) none MeOH (10 equiv) MeOH (10 equiv) MeOH (10 equiv) MeOH (10 equiv)

75 26 4 2 2 13 1 68 0 53 25 59 24 16 20 9 0 81 48 52 4

2 61 72 63 48 36 53 8 0 1 53 1 42 45 53 64 13 11 7 4 83

1 10 18 4 3 16 9 2 0 1 11 1 11 20 18 25 1 0 1 1 4

a

The reaction was performed using 0.15 mmol of 1a and 0.1 mmol of 2a (0.3 M) for 12 h. bDetermined by GC using mesitylene as an internal standard.

opening and exhibited only a minor impact (entries 18−20), while MeOH certainly improved the chemoselectivity of the Co(OAc)2/dppp system toward hydroalkylation (entry 14 vs entry 21). Thus, only when combined with Co(OAc)2, MeOH is effective for the improvement of the selectivity toward hydroalkylation with suppression of the ring opening and annulation (cf. Table 1, entries 11−13). Scheme 4 illustrates proposed reaction pathways for the present alkylative ring-opening and hydroalkylation reactions. Assisted by DABCO, a (diphosphine)CoII species A and cyclopropanol 1 would form a cobalt(II) cyclopropoxide B, followed by ring opening to generate a cobalt(II) homoenolate C.19 Carbocobaltation to the oxabicyclic alkene 2 would give rise to an alkylcobalt species D as a common intermediate.3d,4k,9a β-Oxygen elimination of D leads to the alkylative ring-opening product 3, while protonolysis of D furnishes the hydroalkylation product 4. In addition, D may also undergo intramolecular addition of the alkylcobalt moiety onto the C O bond to afford the cyclized product 5. The difference between the CoCl2- and Co(OAc)2-based catalytic systems is multifold and is nontrivial to fully understand at this moment. These catalytic systems display not only different chemoselectivity with the same substrate but also a distinct response to nitrogen bases used in place of DABCO (vide supra; see Table S4) as well as distinct reactivity toward less reactive oxaand azabicyclic substrates (see 3x/3y in Scheme 2 and 4x/4y in Scheme 3). While we have difficulty in rationalizing the latter features, we are tempted to put forward some working hypotheses on the counterion-dependent chemodivergence

a The reaction was performed on a 0.3 mmol scale. bThe reaction was performed using dppp instead of (R,R)-bdpp.

contrast to the drastic impact of carboxylate salts on the cobalt(II) halide-based catalysts, the addition of a chloride salt such as NaCl or [Bu4N]Cl to the Co(OAc)2/dppp catalytic system did not reverse the preference for hydroalkylation (entries 14−16). Similar observations were made in control experiments using (R,R)-bdpp, while the reactions were accompanied by greater amounts of 5a (Table S6). These observations suggest that a carboxylate anion greatly changes the nature of the CoCl2-derived catalyst, while a chloride anion has little impact on the Co(OAc)2-derived catalyst. In accordance with this conjecture, UV−vis analysis indicated that (diphosphine)CoCl2 undergoes facile displacement of the chloride by an acetate, while (diphosphine)Co(OAc)2 is unaffected by a chloride (Figures S2 and S3). Importantly, the use of cobalt(II) pivalate as a precatalyst also resulted in preferential hydroalkylation albeit in low overall efficiency (entry 17), again underscoring the significant effect of carboxylate counterion on the chemoselectivity. The effect of MeOH also deserves comments. Interestingly, the addition of MeOH (10 equiv) to the cobalt(II) halide/ dppp systems did not overturn the selectivity toward ring 5641

DOI: 10.1021/acscatal.9b00655 ACS Catal. 2019, 9, 5638−5644

Letter

ACS Catalysis Scheme 4. Proposed Reaction Pathways

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Crystallographic data for 4a (CIF)

AUTHOR INFORMATION

Corresponding Authors

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

Naohiko Yoshikai: 0000-0002-8997-3268 Present Address †

Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai 2000438, P.R. China Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Ministry of Education (Singapore, MOE2016-T2-2-043) and Nanyang Technological University. We thank Dr. Yongxin Li (Nanyang Technological University) for his assistance with the X-ray crystallographic analysis.

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(1) (a) Lautens, M.; Fagnou, K.; Hiebert, S. Transition MetalCatalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic Alkenes. Acc. Chem. Res. 2003, 36, 48−58. (b) Lautens, M.; Fagnou, K. Rhodium-Catalyzed Asymmetric Ring Opening Reactions of Oxabicyclic Alkenes: Catalyst and Substrate Studies Leading to a Mechanistic Working Model. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 5455−5460. (c) Rayabarapu, D. K.; Cheng, C.-H. New Catalytic Reactions of Oxa- and Azabicyclic Alkenes. Acc. Chem. Res. 2007, 40, 971−983. (d) Bournaud, C.; Chung, F.; Luna, A. P.; Pasco, M.; Errasti, G.; Lecourt, T.; Micouin, L. Stereoselective Transformations of Meso Bicyclic Hydrazines: Versatile Access to Functionalized Aminocyclopentanes. Synthesis 2009, 2009, 869−887. (2) (a) Lautens, M.; Hiebert, S.; Renaud, J.-L. Enantioselective Ring Opening of Aza and Oxabicyclic Alkenes with Dimethylzinc. Org. Lett. 2000, 2, 1971−1973. (b) Lautens, M.; Renaud, J. L.; Hiebert, S. Palladium-Catalyzed Enantioselective Alkylative Ring Opening. J. Am. Chem. Soc. 2000, 122, 1804−1805. (c) Lautens, M.; Hiebert, S.; Renaud, J. L. Mechanistic Studies of the Palladium-Catalyzed Ring Opening of Oxabicyclic Alkenes with Dialkylzinc. J. Am. Chem. Soc. 2001, 123, 6834−6839. (3) For organozinc reagents, see: (a) Lautens, M.; Hiebert, S. Palladium-Catalyzed Alkylative Ring Opening. J. Am. Chem. Soc. 2004, 126, 1437−1447. (b) Li, M.; Yan, X.-X.; Hong, W.; Zhu, X.-Z.; Cao, B.-X.; Sun, J.; Hou, X.-L. Palladium-Catalyzed Enantioselective Ring Opening of Oxabicyclic Alkenes with Organozinc Halides. Org. Lett. 2004, 6, 2833−2835. (c) Cabrera, S.; Arrayás, R. G.; Alonso, I.; Carretero, J. C. Fesulphos-Palladium(II) Complexes as Well-Defined Catalysts for Enantioselective Ring Opening of Meso Heterobicyclic Alkenes with Organozinc Reagents. J. Am. Chem. Soc. 2005, 127, 17938−17947. (d) Endo, K.; Tanaka, K.; Ogawa, M.; Shibata, T. Multinuclear Pd/Zn Complex-Catalyzed Asymmetric Alkylative RingOpening Reaction of Oxabicyclic Alkenes. Org. Lett. 2011, 13, 868− 871. (e) Li, Y.; Chen, J.; He, Z.; Qin, H.; Zhou, Y.; Khan, R.; Fan, B. Cobalt-Catalyzed Asymmetric Reactions of Heterobicyclic Alkenes with in Situ Generated Organozinc Halides. Org. Chem. Front. 2018, 5, 1108−1112. (4) For organoboron reagents, see: (a) Lautens, M.; Dockendorff, C.; Fagnou, K.; Malicki, A. Rhodium-Catalyzed Asymmetric Ring Opening of Oxabicyclic Alkenes with Organoboronic Acids. Org. Lett. 2002, 4, 1311−1314. (b) Lautens, M.; Dockendorff, C. Palladium(II) Catalyst Systems for the Addition of Boronic Acids to Bicyclic Alkenes: New Scope and Reactivity. Org. Lett. 2003, 5, 3695−3698. (c) Menard, F.; Lautens, M. Chemodivergence in Enantioselective

between the cobalt halide- and carboxylate-based catalytic systems. Thus, β-oxygen elimination of D would require a vacant coordination site on cobalt to interact with the oxygen atom and thus might proceed more efficiently when X was halide rather than chelating carboxylate. On the other hand, HOAc (or other carboxylic acid) generated from Co(OAc)2 or a carboxylate additive (cf. Table 2, entries 2−7) would facilitate protonolysis of the Co−C bond of D through a sixcentered, reverse concerted metalation−deprotonation (CMD) mechanism.11,21 The effect of MeOH on the Co(OAc)2 system to improve the chemoselectivity toward hydroalkylation (cf. Table 2, entries 14 and 21) may be rationalized by its influence on the equilibrium between acetate anion and acetic acid, which would increase the effective concentration of the latter. In summary, we have disclosed cobalt-catalyzed divergent enantioselective reactions between cyclopropanols and oxabicyclic alkenes to afford either alkylative ring-opening products or hydroalkylation products. The chemoselectivity switch was achieved by changing the counterion of the cobalt precatalyst while using the same chiral diphosphine ligand, which granted similar levels of enantioselectivity for both the transformations. To our knowledge, the present reactions are the first examples of homoenolate addition to nonpolar alkenes,22 and they represent rare examples of catalytic enantioselective ringopening transformation of cyclopropanols.18,23 Further synthetic and mechanistic studies on selective catalytic transformations of cyclopropanols and related compounds are currently underway.

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REFERENCES

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b00655. Experimental procedures and spectral data for all new compounds (PDF) 5642

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ACS Catalysis

alkynylation Reactions of Oxabenzonorbornadienes. Org. Biomol. Chem. 2013, 11, 814−820. (c) Bexrud, J.; Lautens, M. A Rhodium Ibiox[(−)-Menthyl] Complex as a Highly Selective Catalyst for the Asymmetric Hydroarylation of Azabicyles: An Alternative Route to Epibatidine. Org. Lett. 2010, 12, 3160−3163. (10) Ito, S.; Itoh, T.; Nakamura, M. Diastereoselective Carbometalation of Oxa- and Azabicyclic Alkenes under Iron Catalysis. Angew. Chem., Int. Ed. 2011, 50, 454−457. (11) Mo, D.-L.; Chen, B.; Ding, C.-H.; Dai, L.-X.; Ge, G.-C.; Hou, X.-L. Switch of Addition and Ring-Opening Reactions of Oxabicyclic Alkenes with Terminal Alkynes by sp2-C,P- and sp3-C,P-Palladacycle Catalysis. Organometallics 2013, 32, 4465−4468. (12) Nikolaev, A.; Orellana, A. Transition-Metal-Catalyzed C-C and C-X Bond-Forming Reactions Using Cyclopropanols. Synthesis 2016, 48, 1741−1768. (13) For recent examples, see: (a) Mills, L. R.; Arbelaez, L. M. B.; Rousseaux, S. A. L. Electrophilic Zinc Homoenolates: Synthesis of Cyclopropylamines from Cyclopropanols and Amines. J. Am. Chem. Soc. 2017, 139, 11357−11360. (b) Tumma, N.; Gyanchander, E.; Cha, J. K. Cu-Mediated Rearrangements of Allenylcyclopropanols to Cyclopentenones: Two Divergent Pathways. J. Org. Chem. 2017, 82, 4379−4385. (c) Zhou, X.; Qi, Z.; Yu, S.; Kong, L.; Li, Y.; Tian, W.-F.; Li, X. Synthesis of 2-Substituted Quinolines via Rhodium(III)Catalyzed C-H Activation of Imidamides and Coupling with Cyclopropanols. Adv. Synth. Catal. 2017, 359, 1620−1625. (d) Liu, H.; Fu, Z.; Gao, S.; Huang, Y.; Lin, A.; Yao, H. Palladium-Catalyzed Hydroalkylation of Alkynes with Cyclopropanols: Access to β,γUnsaturated Ketones. Adv. Synth. Catal. 2018, 360, 3171−3175. (e) Nikolaev, A.; Legault, C. Y.; Zhang, M.; Orellana, A. The AcidFree Cyclopropanol-Minisci Reaction Reveals the Catalytic Role of Silver-Pyridine Complexes. Org. Lett. 2018, 20, 796−799. (f) Reding, A.; Jones, P. G.; Werz, D. B. Intramolecular Trans-Carbocarbonation of Internal Alkynes by a Cascade of Formal Anti-Carbopalladation/ Cyclopropanol Opening. Org. Lett. 2018, 20, 7266−7269. (g) Wu, P.; Jia, M.; Lin, W.; Ma, S. Matched Coupling of Propargylic Carbonates with Cyclopropanols. Org. Lett. 2018, 20, 554−557. (h) Ye, Z.; Cai, X.; Li, J.; Dai, M. Catalytic Cyclopropanol Ring Opening for Divergent Syntheses of Gamma-Butyrolactones and Delta-Ketoesters Containing All-Carbon Quaternary Centers. ACS Catal. 2018, 8, 5907−5914. (14) (a) Yoshikai, N. Recent Advances in Enantioselective C-C Bond Formation via Organocobalt Species. Synthesis 2019, 51, 135− 145. (b) Pellissier, H.; Clavier, H. Enantioselective Cobalt-Catalyzed Transformations. Chem. Rev. 2014, 114, 2775−2823. (15) For recent examples, see: (a) Kim, D. K.; Riedel, J.; Kim, R. S.; Dong, V. M. Cobalt Catalysis for Enantioselective Cyclobutanone Construction. J. Am. Chem. Soc. 2017, 139, 10208−10211. (b) Yang, J.; Rerat, A.; Lim, Y. J.; Gosmini, C.; Yoshikai, N. Cobalt-Catalyzed Enantio- and Diastereoselective Intramolecular Hydroacylation of Trisubstituted Alkenes. Angew. Chem., Int. Ed. 2017, 56, 2449−2453. (c) Yu, S.; Wu, C.; Ge, S. Cobalt-Catalyzed Asymmetric Hydroboration/Cyclization of 1,6-Enynes with Pinacolborane. J. Am. Chem. Soc. 2017, 139, 6526−6529. (d) Chen, M.-H.; Hsieh, J.-C.; Lee, Y.H.; Cheng, C.-H. Controlled Synthesis of Enantioselective 1Aminoindenes via Cobalt-Catalyzed [3 + 2] Annulation Reaction. ACS Catal. 2018, 8, 9364−9369. (e) Pagar, V. V.; RajanBabu, T. V. Tandem Catalysis for Asymmetric Coupling of Ethylene and Enynes to Functionalized Cyclobutanes. Science 2018, 361, 68−72. (f) Pesciaioli, F.; Dhawa, U.; Oliveira, J. C. A.; Yin, R.; John, M.; Ackermann, L. Enantioselective Cobalt(III)-Catalyzed C-H Activation Enabled by Chiral Carboxylic Acid Cooperation. Angew. Chem., Int. Ed. 2018, 57, 15425−15429. (g) Wang, C.; Ge, S. Versatile Cobalt-Catalyzed Enantioselective Entry to Boryl-Functionalized AllCarbon Quaternary Stereogenic Centers. J. Am. Chem. Soc. 2018, 140, 10687−10690. (h) Wu, L.; Shao, Q.; Yang, G.; Zhang, W. CobaltCatalyzed Asymmetric Allylation of Cyclic Ketimines. Chem. - Eur. J. 2018, 24, 1241−1245. (i) Wu, C.; Yoshikai, N. Cobalt-Catalyzed Intramolecular Reactions between a Vinylcyclopropane and an

Desymmetrization of Diazabicycles: Ring-Opening Versus Reductive Arylation. Angew. Chem., Int. Ed. 2008, 47, 2085−2088. (d) Panteleev, J.; Menard, F.; Lautens, M. Ligand Control in Enantioselective Desymmetrization of Bicyclic Hydrazines: Rhodium(I)-Catalyzed Ring-Opening Versus Hydroarylation. Adv. Synth. Catal. 2008, 350, 2893−2902. (e) Zhang, T.-K.; Mo, D.-L.; Dai, L.-X.; Hou, X.-L. Asymmetric Ring-Opening Reaction of Oxabicyclic Alkenes with Aryl Boronic Acids Catalyzed by P-Containing Palladacycles. Org. Lett. 2008, 10, 3689−3692. (f) Crotti, S.; Bertolini, F.; Macchia, F.; Pineschi, M. Rhodium-Catalyzed Enantioselective Desymmetrization of Bicyclic Hydrazines with Alkynylboronic Esters. Chem. Commun. 2008, 3127−3129. (g) Tsui, G. C.; Tsoung, J.; Dougan, P.; Lautens, M. One-Pot Synthesis of Chiral Dihydrobenzofuran Framework Via Rh/Pd Catalysis. Org. Lett. 2012, 14, 5542−5545. (h) Pan, X.; Huang, G.; Long, Y.; Zuo, X.; Xu, X.; Gu, F.; Yang, D. Platinum(II)-Catalyzed Asymmetric Ring-Opening Addition of Arylboronic Acids to Oxabenzonorbornadienes. J. Org. Chem. 2014, 79, 187−196. (i) Zeng, Z.; Yang, D.; Long, Y.; Pan, X.; Huang, G.; Zuo, X.; Zhou, W. Nickel-Catalyzed Asymmetric Ring Opening of Oxabenzonorbornadienes with Arylboronic Acids. J. Org. Chem. 2014, 79, 5249−5257. (j) Yamamoto, T.; Akai, Y.; Suginome, M. Chiral Palladacycle Catalysts Generated on a Single-Handed Helical Polymer Skeleton for Asymmetric Arylative Ring Opening of 1,4-Epoxy-1,4Dihydronaphthalene. Angew. Chem., Int. Ed. 2014, 53, 12785−12788. (k) Huang, Y.; Ma, C.; Lee, Y. X.; Huang, R. Z.; Zhao, Y. CobaltCatalyzed Allylation of Heterobicyclic Alkenes: Ligand-Induced Divergent Reactivities. Angew. Chem., Int. Ed. 2015, 54, 13696− 13700. (l) Zhang, W.; Chen, J.; Zeng, G.; Yang, F.; Xu, J.; Sun, W.; Shinde, M. V.; Fan, B. Asymmetric Ring-Opening Reactions of Azaand Oxa-Bicyclic Alkenes with Boronic Acids Using a Palladium/Zinc Co-Catalytic System. J. Org. Chem. 2017, 82, 2641−2647. (5) For terminal alkynes, see: (a) Nishimura, T.; Tsurumaki, E.; Kawamoto, T.; Guo, X. X.; Hayashi, T. Rhodium-Catalyzed Asymmetric Ring-Opening Alkynylation of Azabenzonorbornadienes. Org. Lett. 2008, 10, 4057−4060. (b) Fan, B.; Li, S.; Chen, H.; Lu, Z.; Liu, S.; Yang, Q.; Yu, L.; Xu, J.; Zhou, Y.; Wang, J. Palladium/Copper Complexes Co-Catalyzed Highly Enantioselective Ring Opening Reaction of Azabenzonorbornadienes with Terminal Alkynes. Adv. Synth. Catal. 2013, 355, 2827−2832. (6) For the reaction of indole derivative via C−H activation, see: Yang, X.; Zheng, G.; Li, X. Rhodium(III)-Catalyzed Enantioselective Coupling of Indoles and 7-Azabenzonorbornadienes by C-H Activation/Desymmetrization. Angew. Chem., Int. Ed. 2019, 58, 322−326. (7) For copper-catalyzed reactions featuring anti-selectivity, see: (a) Bertozzi, F.; Pineschi, M.; Macchia, F.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L. Copper Phosphoramidite Catalyzed Enantioselective Ring-Opening of Oxabicyclic Alkenes: Remarkable Reversal of Stereocontrol. Org. Lett. 2002, 4, 2703−2705. (b) Zhang, W.; Wang, L.-X.; Shi, W.-J.; Zhou, Q.-L. Copper-Catalyzed Asymmetric Ring Opening of Oxabicyclic Alkenes with Grignard Reagents. J. Org. Chem. 2005, 70, 3734−3736. (c) Bos, P. H.; Rudolph, A.; Pérez, M.; Fañanás-Mastral, M.; Harutyunyan, S. R.; Feringa, B. L. CopperCatalyzed Asymmetric Ring Opening of Oxabicyclic Alkenes with Organolithium Reagents. Chem. Commun. 2012, 48, 1748−1750. (8) For recent examples involving soft carbon nucleophiles with antiselectivity, see: (a) Zhang, L.; Le, C. M.; Lautens, M. The Use of Silyl Ketene Acetals and Enol Ethers in the Catalytic Enantioselective Alkylative Ring Opening of Oxa/Aza Bicyclic Alkenes. Angew. Chem., Int. Ed. 2014, 53, 5951−5954. (b) Loh, C. C. J.; Fang, X.; Peters, B.; Lautens, M. Benzylic Functionalization of Anthrones via the Asymmetric Ring Opening of Oxabicycles Utilizing a FourthGeneration Rhodium Catalytic System. Chem. - Eur. J. 2015, 21, 13883−13887. (9) (a) Sawano, T.; Ou, K.; Nishimura, T.; Hayashi, T. CobaltCatalyzed Asymmetric Addition of Silylacetylenes to Oxa- and Azabenzonorbornadienes. Chem. Commun. 2012, 48, 6106−6108. (b) Hu, J.; Yang, Q.; Xu, J.; Huang, C.; Fan, B.; Wang, J.; Lin, C.; Bian, Z.; Chan, A. S. C. Iridium-Catalyzed Asymmetric Hydro5643

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Letter

ACS Catalysis Alkyne: Switchable [5 + 2] Cycloaddition and Homo-Ene Pathways. Angew. Chem., Int. Ed. 2018, 57, 6558−6562. (16) (a) Gao, K.; Yoshikai, N. Low-Valent Cobalt Catalysis: New Opportunities for C-H Functionalization. Acc. Chem. Res. 2014, 47, 1208−1219. (b) Wu, J.; Yoshikai, N. Cobalt-Catalyzed Alkenylzincation of Unfunctionalized Alkynes. Angew. Chem., Int. Ed. 2016, 55, 336−340. (c) Yang, J.; Yoshikai, N. Cobalt-Catalyzed Annulation of Salicylaldehydes and Alkynes to Form Chromones and 4-Chromanones. Angew. Chem., Int. Ed. 2016, 55, 2870−2874. (d) Ding, W.; Yoshikai, N. Cobalt-Catalyzed Intermolecular [2 + 2] Cycloaddition between Alkynes and Allenes. Angew. Chem., Int. Ed. 2019, 58, 2500− 2504. (17) (a) Gandeepan, P.; Cheng, C.-H. Cobalt Catalysis Involving Pi Components in Organic Synthesis. Acc. Chem. Res. 2015, 48, 1194− 1206. (b) Moselage, M.; Li, J.; Ackermann, L. Cobalt-Catalyzed C-H Activation. ACS Catal. 2016, 6, 498−525. (c) Röse, P.; Hilt, G. Cobalt-Catalysed Bond Formation Reactions; Part 2. Synthesis 2016, 48, 463−492. (18) Yang, J.; Shen, Y.; Lim, Y. J.; Yoshikai, N. Divergent RingOpening Coupling between Cyclopropanols and Alkynes under Cobalt Catalysis. Chem. Sci. 2018, 9, 6928−6934. (19) Yang, J.; Sun, Q.; Yoshikai, N. Cobalt-Catalyzed Regio- and Diastereoselective Formal [3 + 2] Cycloaddition between Cyclopropanols and Allenes. ACS Catal. 2019, 9, 1973−1978. (20) CCDC 1863537 (4a) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre. (21) (a) Lapointe, D.; Fagnou, K. Overview of the Mechanistic Work on the Concerted Metallation-Deprotonation Pathway. Chem. Lett. 2010, 39, 1118−1126. (b) Ackermann, L. Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope. Chem. Rev. 2011, 111, 1315−1345. (22) (a) Kuwajima, I.; Nakamura, E. Metal Homoenolates from Siloxycyclopropanes. Top. Curr. Chem. 1990, 155, 3−39. (b) Kuwajima, I.; Nakamura, E. In Comprehensive Organic Synthesis; Trost, B., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 2, p 4411. (23) Trost, B. M.; Yasukata, T. A Catalytic Asymmetric WagnerMeerwein Shift. J. Am. Chem. Soc. 2001, 123, 7162−7163.

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DOI: 10.1021/acscatal.9b00655 ACS Catal. 2019, 9, 5638−5644