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. 2026 Jan 7;148(2):2810–2819. doi: 10.1021/jacs.5c20554

Asymmetric Desymmetrizing Sulfonylation of Diarylmethanes via Peptidyl-Cu(I)-Catalysis with Remote Stereocontrol

Hyun-Suk Um 1, Scott J Miller 1,*
PMCID: PMC12833865  PMID: 41499463

Abstract

An asymmetric catalytic desymmetrizing cross-coupling of diarylmethanes with organosulfinates has been developed. Permutations of proteinogenic and noncanonical amino acids allow access to guanidinylated peptide-based ligands that may be tuned for distal stereocontrol under copper catalysis. Noncovalent attractive interactions are likely significant in organizing the geometry of substrate–copper–peptide ternary complexes, modulated by countercation effects, for effective enantioselective oxidative addition; further enantioenrichment of the sulfone products occurs via secondary kinetic resolution, corroborated by mechanistic studies. The mild protocols disclosed herein expand asymmetric and site-selective catalysis mediated by peptides first to enable C–S bond-forming cross-coupling reactions with remote stereocontrol.

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Introduction

Synthesis of enantiomerically enriched molecules has become a foremost aspiration in the field of organic chemistry. Pivotal among diverse endeavors is asymmetric transition-metal catalysis, from which high levels of stereoselectivity can be imparted from chiral metal complexes to substrates in a vast array of reactions. In addition to steric control strategies based on chiral ligands, ensembles of noncovalent interactions are now commonly employed to deliver stereoselectivity. Inspired in part by enzymes, small organic molecules represented by low molecular weight peptides have also been shown to induce chiral environments in a biomimetic manner. Often, the creation of new stereogenic elements occurs along with or proximal to newly formed bonds. On the other hand, cases of remote asymmetric induction remain less common, although important advances have been noted with chiral catalysts. In this context, asymmetric access to diarylmethane scaffolds is particularly desirable grounded on their privileged role in medicinal chemistry. Peptide-based organocatalysts were found to be well-suited to this challenge in acylation and bromination reactions of diarylmethanes (Figure A). In more recent highlights, Yu pioneered metal-catalyzed C–H bond functionalizations with diarylmethanes, while Phipps unveiled remote asymmetric C–H bond functionalizations and cross-couplings based on ionic interactions between catalysts and these scaffolds (Scheme B; left section). Zhu expanded the field to include powerful examples that fashioned quaternary centers bridging the diarylmethane substituents (Scheme B, right section). , In our lab, we showed guanidinylated peptides to be effective ligands for use in asymmetric desymmetrizing cross-coupling reactions of diarylmethanes under copper catalysis (Figure C). While guanidinylated peptides are versatile for a diverse range of cross-coupling reactions including C–C, C–O, , C–N, , and C–I bond-forming processes, their applicability to catalytic enantioselective construction of C–S linkages remains elusive to the best of our knowledge.

1.

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Catalytic asymmetric desymmetrization of diarylmethanes.

1. Reaction Optimization.

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Of particular importance among organosulfur compounds are sulfonyl derivatives that constitute scaffolds in a wide variety of pharmaceuticals, agrochemicals, and organic materials. Distinct from the O–S bond formation approaches such as oxidation and nucleophilic organocatalysis, accessing sulfones by means of forging C–S bonds has become a compelling synthetic strategy, contemporary research foci of which principally aim at developing and exploiting sulfur dioxide surrogates such as DABSO and metal sulfite salts. In addition, use of organosulfinates for the synthesis of sulfones has served as salient modi operandi grounded on their commercial availability, easy accessibility, and broad applicability. Motivated by the precedents with organosulfinates for coupling with aryl halides under copper catalysis, we envisioned that sulfonylative desymmetrization of diarylmethanes with remote asymmetric induction might be feasible through catalytic enantioselective C–S bond construction mediated by peptidyl copper complexes. Distinct from the well-documented capability of organosulfur functionalities to effect distal stereocontrol in an intramolecular fashion with chiral auxiliary strategies, to our surprise, intermolecular coupling of an organosulfur species commensurate with remote asymmetric induction has not been reported to date. We disclosed herein our studies on the development of asymmetric desymmetrizing cross-coupling of diarylmethanes with sulfinic acid salts for C–S bond formation in the presence of copper catalysts supported by multifunctional guanidinylated peptides.

Results and Discussion

Inspired by the seminal report by Ma and co-workers, we began with a test of l-proline as a ligand in the copper-catalyzed sulfonylation with diarylmethane 1. Gratifyingly, the reaction of 1 with sodium p-toluenesulfinate took place to furnish the mono-sulfonylated diarylmethane 2a in an isolated yield of 20%. Use of a single amino acid, l-proline, sufficed to induce low but detectable stereocontrol (9% ee). Grounded on the promising results (omitted for clarity; see Supporting Information for details), our studies directly transitioned to guanidinylated amino acids such as L1 as a model ligand in the copper-catalyzed asymmetric desymmetrizing sulfonylation of diarylmethane 1. Systematic investigations of each variable for the reaction revealed that the solvent is of paramount importance for stereocontrol (Scheme and Table S4). Among the solvents examined, the reaction proceeded smoothly in polar aprotic solvents, as expected (Scheme , entries 1–4). Most notably, when acetonitrile was introduced as solvent, a trace amount of the desired mono-sulfonylated product 2 was isolated, but with high enantioselectivities over 90% ee (entry 5). Asymmetric C–S bond construction could also be achieved at lower temperature as pioneered by Ma for substrates with ortho-trifluoroacetamide substituents. Accordingly, when the reaction temperature was lowered from 90 °C to 50 °C, product 2a could be obtained in 49% yield, and with 10:90 er (entry 6 and Tables S5–S6). Although the accelerating effect induced by ortho-trifluoroacetamide groups has been manifested in other Ullmann-type cross-coupling reactions, its applicability to C–S bond-forming processes has not been reported, to the best of our knowledge. Under the milder reaction conditions, the major unproductive pathways (hydrolysis of sulfonylated products 2 and 3; see Scheme S1 in Supporting Information for details) could be averted, which enhances the overall reaction efficacy (entry 5 vs entry 6). It should be noted that this sulfonylative cross-coupling process is uncommonly facile, and high stereoselectivities benefit from secondary kinetic resolution (vide infra).

Through a series of screening experiments, it was found that the reaction could be effectively carried out under inert Ar conditions employing 10 mol % Cu­(MeCN)4BF4, 20 mol % L1, 1.2 equiv of p-TolSO2Na, and 4 equiv of K3PO4 in MeCN (0.5 M) at 50 °C for 2 h (Scheme , Condition B). Having identified the optimal reaction conditions for asymmetric desymmetrizing sulfonylation with L1, we next probed peptides based on higher order structures. To our delight, all trimeric and tetrameric peptides L2–5 exhibited increased selectivities targeting 2a in terms of both yield and er compared to L1 (entry 7 vs entries 8–11). Superior among the peptides examined was L4 (entry 10), which was then selected as the lead ligand for S-nucleophiles, delivering 2a in 72% isolated yield and with 4:96 er, extending its role beyond the demonstrated applicability to N-nucleophiles. ,

With the optimized conditions featuring peptide L4 in hand, we then examined the scope of the reaction with an assortment of sulfinic acid sodium salts (Table ). Indeed, a variety of aryl (2a–c), alkyl (2d–f), and heteroaryl (2g–i) sulfonyl motifs could be installed to diarylmethane 1 with excellent enantioselectivities. Sodium p-toluenesulfinate, the nucleophile used for the optimization studies, afforded the mono-sulfonylated product 2a in 62% isolated yield with 96% ee along with the bis-sulfonylated product 3a in 21% NMR yield. Sodium salts of benzene- and 4-bromobenzene-sulfinic acid could also furnish the chiral aryl sulfones 2b and 2c in 56% and 54% yields, respectively. Although the isolated yields of the aryl sulfone products were slightly diminished compared to the case of 1a, possibly due to the attenuated nucleophilicity of the sulfinates, the observed enantioselectivities remained high (95% ee for 2a vs 97% ee for 2b and 2c), reflecting an increase in asymmetric induction relative to 2a. In addition, product 2c reveals that an aryl bromide functionality devoid of an ortho-trifluoroacetamide group is tolerated under mild conditions, allowing a site-selective cross-coupling reaction (vide infra). Next, synthesis of chiral alkyl sulfones could also be successfully accomplished, as demonstrated with methyl (2d; 66%, 95% ee), iso-propyl (2e; 64%, 91% ee) and tert-butyl (2f; 54%, 89% ee) sulfone products, respectively. It is noteworthy that as the steric demand of alkyl sulfinates increases, both yields and enantioselectivities decrease slightly. Noticeable among these examples is the stark contrast in selectivity exhibited by 2c and 2f, both of which did not significantly benefit from secondary kinetic resolution (97% ee for 2c with 10% of 3c vs 89% ee for 2f with 6% of 3f). We postulate that developing the steric bulk of organosulfinate nucleophiles may impede the catalytic C–S bond formation process through reductive elimination as well as distort the geometry of catalytic intermediates in the enantio-determining step. Subsequently, enantioselective synthesis of pyridyl sulfones was pursued, seeking to explore the compatibility of nitrogen heterocycles, common in pharmaceuticals, with the chemistry. Incorporation of a nitrogen atom in various positions did not hamper the mode of asymmetric catalysis, as 2-pyridyl (2g; 61%, 96% ee), 3-pyridyl (2h; 61%, 96% ee), and 4-pyridyl (2i; 57%, 94% ee) sulfones were all obtained in a highly selective fashion, respectively. In addition, sodium 3-methoxy-3-oxopropane-1-sulfinate (SMOPS) was proved to be a competent S-nucleophile, generating sulfone 2j in 39% isolated yield with 91% ee. The resulting alkyl sulfone derived from the commercially available sulfinate reagent could be capable of further derivatizations into alkyl sulfones, aryl sulfones, sulfonamides, and sulfonyl fluorides, respectively. When sodium thiophene-2-sulfinate was introduced, however, the reaction became sluggish only to furnish the desired sulfone product (2k; 31%, 80% ee) along with 1 (63%) within 2 h; it is possible that a stable copper complex, as in the case of CuTC, copper­(I) thiophene-2-carboxylate, is formed.

1. Copper-Catalyzed Asymmetric Desymmetrizing Sulfonylation of Diarylmethanes with Organosulfinates .

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a

All reactions were carried out with 0.1 mmol of 1. Yields and enantioselectivities of 2 were obtained after purification while yields of 3 (and 1, where applicable) were determined by NMR yields based on integration against 1,4-bis(trimethylsilyl)­benzene. All of the documented data are the average of two independent trials. The enantiomeric ratio (er) was listed in order of elution and the major stereoisomers were displayed. The absolute configuration of 2c was unambiguously determined via single crystal X-ray diffraction.

In our continuing efforts, a few limitations have also been identified. Direct access to a triflone scaffold was not feasible when the Langlois’ reagent, CF3SO2Na, was employed as the nucleophile, perhaps due to the low nucleophilicity and relatively mild reaction conditions. Despite a success with SMOPS, no reaction occurred with TBS-protected hydroxymethanesulfinate, known for its versatile derivatization utility, presumably because of the significantly more heterogeneous mixture in MeCN. Lastly, introducing a pyrimidyl or benzothiazoyl sulfone, the versatile structural motif, to diarylmethane 1 was not viable under the optimized conditions.

Next explored was the structural evaluation of diarylmethane electrophiles. As a sterically bulky substituent at the prochiral carbon center has proved to be essential for remote asymmetric induction with many diarylmethane derivatizations, a tert-butyl group could be replaced by a methylcyclohexyl moiety with a comparable level of selectivities (2l; 68%, 96% ee). However, a less sterically demanding cyclohexyl group was manifested in a lower level of enantiocontrol (2m; 48%, 84% ee).

Having established the scope of asymmetric desymmetrizing sulfonylation, we explored some mechanistic aspects of the catalytic process (Scheme ). Secondary kinetic resolution was confirmed to be operative in catalytic remote stereocontrol through a time course study (Scheme A). It is particularly notable that the mild conditions developed for the sulfonylative cross-coupling, which is generally achieved under more forcing conditions, allowed the optical purity of the resulting sulfone products to be easily enriched. Thus, while the tosylated diarylmethane 2a was obtained in 62% yield with 95% ee under the optimized conditions, the stereoselectivity could be augmented to >99% ee when the reaction was carried out for 4 h instead of 2 h. Further enantioenrichment of 2m, which suffered from diminished enantioselectivity due to the lower steric demands of the methine substituent, could also be achieved by extending the reaction time from 2 h (84% ee) to 24 h (93% ee). This protocol underscores an ease of operation that allows the enantioenrichment of several intrinsically less selective substrates.

2. Mechanistic Investigations.

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In addition, preliminary screening experiments substantiated the indispensability of base (Scheme B) and also suggested the involvement of countercation such as Cs+, K+, and Na+ in asymmetric induction (Tables S2, S7 and S8), consistent with our previous disclosure. In this context, when the zinc salt of iso-propylsulfinic acid was exploited as a coupling partner, the efficacy of the reaction targeting 2e was reduced, in comparison to the case of the corresponding sodium sulfinate (38% yield and 82% ee vs 64% yield and 91% ee). The modest result may be attributed to the diminished reactivity of homo- and heteroleptic zinc sulfinates and minimal secondary kinetic resolution, indirectly supported by the remaining starting material 1 (ca. 40%); however, it may also be that the competitive action of the zinc cation in stereocontrol is less efficient.

Further examination of an ortho-substituent effect unveiled the unique involvement of the trifluoroacetamide group. Other amide analogues, such as trichloroacetamides (1n) and trifluoromethanesulfonamide (1o) were not competent substrates for the reaction (Scheme C). On the other hand, 4-acetamidobenzenesulfinic acid sodium salt did engage in the catalytic desymmetrizing C–S bond-forming reaction to afford sulfone 2p in 66% yield with 83% ee. As some starting material was observed in this reaction (1, 19%), introduction of an acetamide functionality to the sulfinate nucleophile seems to influence the reaction rate. Notable from the standpoint of chemoselectivity, no amidation product via para-N-arylation was observed. ,

The detailed basis of the enantioselectivity of these remote desymmetrizations remains elusive. However, in light of the experimental evidence, we surmise that the catalytic asymmetric sulfonylation reaction may proceed through a speculative model, illustrated in Scheme C. Specifically, the copper­(I) precatalyst is first complexed with a guanidinylated aspartic acid residue of peptide L4. Subsequent transmetalation may generate the sulfinato copper­(I) complex presumably bound to sulfur, which undergoes oxidative addition with diarylmethane 1. In these processes, no reaction occurs in the absence of base or without the trifluoroacetamide group (Scheme B,C), which suggests that diarylmethanes equipped with the deprotonated trifluoroacetamide functionalities participate in the sulfonylation reaction. The N- or O-binding mode of the trifluoroacetamide group is not known at this time. Nevertheless, we conjecture that the enantioselectivity of the reaction is imparted through an intricate, multivalent substrate–copper–peptide complex, which may include four countercations per Cu center; ensembles of noncovalent interactions such as ionic and cation−π interactions are likely operative, involving deprotonated trifluoroacetamide groups and the carboxylate group at the C-terminus of peptide L4. The peptide ligand may be able to maintain a β-turn-biased architecture through intramolecular hydrogen-bonding. , In terms of the substrate, the most effective molecular recognition occurs with diarylmethane substrates bearing a bulky substituent at the prochiral carbon center (see Scheme B for the X-ray crystal structure of 1). Eventually, enantioselective oxidative addition takes place, followed by reductive elimination, to afford the mono-sulfonylated product (R)-2 as a major stereoisomer. As presented above, further enantioenrichment is also attained through secondary kinetic resolution (Scheme A). Notwithstanding our putative model, many details remain to be learned, and further studies will be disclosed in due course.

3. Synthetic Applications toward Unsymmetrically Sulfonylated Diaryl Scaffolds.

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Having established the scope of asymmetric desymmetrizing sulfonylation, we further explored the synthetic utility of the protocol (Scheme ). Next, the prowess of guanidinylated peptide L4 as a ligand for copper-catalyzed cross-coupling reactions with diverse heteroatom nucleophiles was demonstrated (Scheme A). When diarylmethane 1 was subjected to the standard conditions with 4-bromobenzenesulfinic acid sodium salt for 2 h, and then exposed to 4-methoxyphenol for 15 h, unsymmetrically bis-functionalized diarylmethane 4 was expediently synthesized in a single pot with high enantioselectivity (94% ee) albeit in modest yield (22% isolated yield for 2 steps, compromised slightly by challenging chromatographic separation; see Supporting Information for details).

Subsequently, site-selective sulfonylation of polybrominated aromatic compounds was investigated (Scheme B). To this end, unsymmetrically brominated diarylmethane 5 was first examined (Scheme B, top). A selective cross-coupling targeting a bromide ortho to the trifluoroacetamide directing group was achieved via site-selective oxidative addition to furnish the mono-sulfonylated diarylmethane 6 as the exclusive product in 81% yield, even when dl-proline, in lieu of guanidinylated peptides, served as a ligand.

To further scrutinize site-selective catalysis, polybrominated diaryl ether 8 was subjected to optimal reaction conditions with either dl-proline or peptide L4. We wondered whether the positional selectivity of the enantioselective desymmetrization might translate to site-selectivity in substrates where the regioisomeric disposition of the bromide substituents might be analogous, but within substrates wherein a stereogenic center was absent (Scheme B, middle). However, no significant site-selectivity, promoted by the peptidyl copper complex, was observed, indicating that inherent substrate control overrode catalyst control. The unperturbed site-selectivity might be in part attributed to electronic control of the polybrominated substrate as well as disparate conformations between l and 8, considering the organized geometry of diarylmethane induced by extensive steric bulk such as a tert-butyl group was essential for efficient enantioinduction.

Lastly, any scale-dependent behavior of the protocol was examined (Scheme B, bottom). Indeed, the copper-catalyzed asymmetric desymmetrizing sulfonylation was readily scalable to a 1 mmol-scale reaction, affording sulfone 2c without any decrease in stereoselectivity (48% yield and 97% ee for a 1.0 mmol scale vs 54% yield and 97% ee for a 0.1 mmol scale; cf. Table ). Of additional note is that while the bis-sulfonylated product 3c was observed, an aryl bromide appended to a para-position without a directing group remained intact even at a large scale reaction, corroborating site-selective catalysis controlled by the ortho-substituent effect.

Conclusions

In summary, we have developed a copper-catalyzed asymmetric desymmetrizing sulfonylation of diarylmethanes in the presence of guanidinylated peptides as ligands. The robust and mild protocol can be scalable up to a 1 mmol scale and applicable to an array of organosulfinates. Versatility of guanidinylated peptides has further been validated by mediating a challenging C–S bond-forming process at the locus four-atom-distal to the stereogenic center in an asymmetric fashion by breaking the symmetry of diarylmethanes. Preliminary studies corroborate that secondary kinetic resolution is also operative to reinforce stereoselectivity, which can be further exploited for enantioenrichment when necessary. Although we were able to achieve site-selective cross-coupling in simple cases such as 2c and 5, it is clear that additional understanding of these catalytic systems is required to effectuate site-selectivity in a more complicated case as in 8. Nevertheless, the accomplishment of previously unprecedented catalytic enantioselective desymmetrization through demanding sulfonylation provides both new capability for asymmetric synthesis and a path forward for the study of site-selective cross-couplings.

Supplementary Material

ja5c20554_si_001.pdf (10.2MB, pdf)
ja5c20554_si_002.zip (55.2MB, zip)

Acknowledgments

This work was supported by the National Institute of General Medical Sciences of the United States National Institutes of Health (NIGMS R35 132092). H.-S.U. gratefully acknowledges the National Research Foundation of Korea for a postdoctoral fellowship (RS-2023-00245642). This research made use of the Chemical and Biophysical Instrumentation Center (CBIC) at Yale University (RRID: SCR_021738). We thank Dr. Paul O. Peterson (Yale University) for insightful discussion, Dr. Fabian S. Menges (Yale University) for HRMS analysis, and Dr. Brandon Q. Mercado (Yale University) and Dr. Sebastian M. Krajewski (Yale University) for SC-XRD analysis. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health or the National Research Foundation of Korea.

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c20554.

  • Experimental details with raw data for all compounds (PDF)

  • A compilation of primary data files (ZIP)

The authors declare no competing financial interest.

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