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DOI: 10.1055/a-1277-8669
Halonium Catalysis: An Underutilized and Underexplored Catalytic Concept in Olefin Functionalizations
Research reported in this publication was supported by the National Institute of General Medical Sciences of the National Institutes of Health (Award Number R15GM139156). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank the University of Toledo for an internal seed grant from the Summer Research Awards and Fellowship Programs.
We dedicate this work to the memory of Professor Kilian Muñiz
Abstract
Iodonium catalysis is described here to accomplish an intermolecular olefin oxyamination reaction. Urea is used as the O- and N-source to add across both activated and unactivated alkenes in a regioselective manner. Mechanistic studies confirm the presence of an iodonium intermediate.
1 Introduction
2 Hypothesis
3 Optimizations and Scope
4 Mechanistic Probes
5 Future Outlook
#
Key words
iodonium catalysis - olefin oxyamination - regioselective - N-heterocycles - oxazolines - aminooxygenationIntroduction
Three-membered cyclic halonium (haliranium), first proposed by Roberts and Kimball, is a classic intermediate often taught in undergraduate organic chemistry courses to account for the trans-addition of a nucleophile and a halogen across an alkene.[2] Structural validation of these intermediates by Olah based on NMR studies, followed by affirmation from Wyndberg, Brown, Nugent, and Kochi based on syntheses from the adamantylideneadamantane system elucidated the distinct structural features and reactivities of the haloniums (Scheme [1a]).[3] Later on, variable-temperature 1H NMR studies by Brown and a series of elegant enantiospecific acetolysis experiments by Denmark revealed the existence of an intriguing olefin-to-olefin transfer process that shed light on the challenges often encountered in the development of enantioselective halofunctionalization reactions (Scheme [1b]).[4] In conjunction with these excellent works, synthetic utilizations of halonium intermediates have been broadly studied and applied in many chemo-, regio-, and stereoselective settings.[5] An area of research involving halonium that may have been overlooked is its capacity to function as a catalytic intermediate. A distinction must be made between halonium catalysis and the abundant literature of halofunctionalization reactions where the halogen is often incorporated in the final product structure.[6] Halonium catalysis refers to the catalytic generation of a halonium intermediate that proceeds to the product formation without the presence of the halogen in the final product. While this concept was first conceptualized by the late professor Kilian Muñiz, examples in this area are rather rare.[7] To the best of our knowledge, these few examples include the work by Muñiz and coworkers that demonstrated an alkene diamination reaction based on bromonium catalysis (Scheme [1c]).[8] In other cases, Zhdankin and coworkers disclosed the cyclopropanation and aziridination of alkenes using catalytic hypoiodite proceeding via the key catalytic iodonium intermediate (Scheme [1d]).[9]
Alexander K. Vogel is a native of Toledo and a current senior undergraduate student at the University of Toledo. His research work focuses on the synthesis of firefly luciferin analogues to examine their photochemical properties.
Elizabeth C. Ziegelmeyer is a junior undergraduate student at the University of Toledo. Her current research focuses on the catalytic utilization of iodonium intermediates.
Eric Cheng is a sophomore undergraduate student at Miami University (OH). He conducted research on alkene difunctionalizations in the research group during the summer of 2019.
Fan Wu obtained his PhD from the University of Toledo studying alkene difunctionalization methods for heterocycle synthesis. He is currently a research faculty at Ningbo University, where his research work focuses on the development of late-stage functionalization strategies on bioactive molecules and natural products.
Leo P. Roberts is a sophomore undergraduate student at the University of Toledo, where his research focuses on the synthesis of firefly luciferin analogues.
Megan M. Vesoulis is a freshman undergraduate student at the University of Toledo. Her research involves the catalytic utilization of iodonium intermediates.
Wei Li obtained his PhD (Prof. John Montgomery) at the University of Michigan studying nickel-catalyzed coupling reactions. Following his postdoctoral studies (Prof. David W. C. MacMillan) at Princeton University on C–N bond formations and photoredox catalysis, he began his independent career at the University of Toledo in 2015, where his group is dedicated to the discovery and development of new catalytic avenues to facilitate access to pharmaceuticals.
Considering that alkene difunctionalization is a powerful strategy for the rapid assembly of molecular complexity as demonstrated by the recent works from a number of groups, the lack of examples involving halonium catalysis in this area is perplexing.[10] In this regard, alkene oxyamination is among the most studied catalytic reactions due to the prevalence of the resulting vicinal oxyamine products in bioactive molecules and ligand frameworks.[11] Inspired by the venerable osmium-catalyzed Sharpless oxyamination protocol, a range of useful catalytic protocols has been developed to circumvent several inherent challenges encountered in the Sharpless protocols.[12] [13] Despite these efforts, regioselectivity for intermolecular oxyamination, in general, remains a complex challenge for this class of reactions.[14] While biased alkenes only provide one regioisomeric outcome, unbiased alkenes often result in regioisomeric mixtures. On this subject, limited but notable examples from Stahl, Yoon, and Xu provide useful solutions for regioselective intermolecular oxyamination reactions (Scheme [2]).[15] In addition, recent advances in directing group strategies provide another alternative for tackling the regioselectivity challenges; however, undirected olefin substrates remain highly problematic.[16]
# 2
Hypothesis of Halonium as a Catalytic Template
With these observations in mind, our group is interested in the utilization of halonium as a catalytic and regiochemical template for intermolecular alkene oxyaminations to access nitrogen-containing heterocycles.[17] As documented in a recent literature, N-heterocycles are highly prevalent motifs in pharmaceuticals, natural products, and agrochemicals, which accounted for close to 60% of all the FDA-approved small-molecule drugs.[18] With respect to the research work here, a number of prominent bioactive molecules such as arabinose aminooxazoline, aminooxazoline xanthene, and allosamidin core, all contain an interesting 2-aminooxazoline framework (Figure [1]).[19]
To facilitate the catalytic utilization of the halonium, a key concept that we have developed in our laboratory is the use of a simple bifunctional and soft nucleophile (tethered nucleophiles A and B, Scheme [3a]).[20] The highly electrophilic nature of the halonium C renders the initial addition of the soft nucleophile feasible. This initial step also constitutes the crucial regiodetermining step. Following this initiation, an intramolecular cyclization process by the now attached bifunctional nucleophile affords a cyclic product.[21] Meanwhile, the two-step nucleophilic additions return the halide catalyst precursor back into the reaction. To close the catalytic cycle, the halide can undergo oxidation to regenerate the requisite halonium ion. Another critical feature of using the bifunctional reagent is that, ideally, the strength of the two nucleophilic components can be differentiated, thus leading to a regioselective outcome. This provides an interesting solution to the regiochemical challenges often encountered in intramolecular or three-component coupling processes as outlined in Scheme [3b] and 3c, respectively.[22] The successful execution of this strategy will therefore provide us an opportunity to recognize halonium as a valuable catalytic and regiochemical template in olefin difunctionalizations.
# 3
Optimizations and Scope
Initially, we tested urea as the bifunctional nucleophile using stoichiometric amounts of simple halogen sources such as I2 or NIS. In general, these conditions afforded less than 10% yield of the desired product.[23] Our catalytic conditions screening on the other hand revealed that pairing LiI and Selectfluor as the catalyst and oxidant combination was more efficient in affording the product. In this case, a facile salt metathesis would produce a highly electrophilic iodenium ion D that can engage soft nucleophiles such as urea as the bifunctional reagent (Scheme [4a]). Coincidentally, our previous works suggested that aerobic oxidation of iodide salts often produced the less electrophilic triiodide intermediates.[24] While the less electrophilic triiodide intermediate could tolerate electron-rich amines and carboxylates as nucleophiles in alkene difunctionalizations, softer nucleophiles were often problematic when utilizing such an oxidative approach. With this optimal catalyst and oxidant combination, we carefully evaluated other factors for the standard alkene substrate 1 and urea 2. Our final conditions are shown in Scheme [4b]. The high temperature facilitated the solubility of the LiI catalyst. More excitingly, only one regioisomeric product 3 was observed. In this case, the nitrogen atom of the urea was added to the benzylic position whereas the oxygen atom was added to the homobenzylic position. Furthermore, control reactions revealed the necessity of both the halide catalyst and the oxidant.
With these conditions in hand, a range of alkene and urea substrates was tested showing excellent regioselectivity and efficiency (>45 substrate examples). A number of representative substrates 4–9 are listed in Scheme [5]. In particular, a notable divergent regiochemical feature was observed here. In this case, the electronically activated olefins often afforded a single regioisomeric product, in which the more nucleophilic nitrogen atom of the urea was added to the electronically activated carbon position, and the oxygen atom of the urea was attached to the other carbon atom (Scheme [5], product 4). Distinctively for the unactivated olefin substrates, the opposite regioisomer relative to N vs. O additions was observed (Scheme [5], product 7). In this case, the more nucleophilic nitrogen atom was added to the less sterically hindered carbon (terminal) position and the oxygen atom to the internal position, which suggests that steric hindrance is the predominant regiochemical factor for the key iodonium intermediate. Currently, one limitation for this method is that while monosubstituted olefins provide the products in excellent yields, di- or trisubstituted unactivated olefins are not efficient substrates in this protocol, often resulting in <20% yield. Despite this drawback, this reaction could tolerate olefin substrates with more complex structures (Scheme [5], products 5, 6, 8, 9).
# 4
Mechanistic Probes
To validate the catalytic involvement of the iodonium in this reaction, we utilized a stereospecificity test, in which the product stereoselectivities of the trans- and cis-β-methylstyrene substrates were examined in separate reactions (Scheme [6a]). For trans-β-methylstyrene, >95:5 dr was observed while the cis-β-methylstyrene afforded the product in 26:74 dr (trans 3/cis 10). Furthermore, a control reaction with cis-β-methylstyrene in the absence of the urea nucleophile resulted in nearly complete stereoerosion under otherwise identical conditions. This control reaction suggests that stereoerosion of the starting material must be taken into consideration. Alarmed by this result, we then examined trans- and cis-4-octene substrates in these reactions. Although the yields were low, the cis-4-octene afforded exclusively the cis-product. In addition, control reactions revealed that stereoerosion of cis-4-octene had not taken place. These reactions validated that carbocation and radical pathways are unlikely here, as these pathways will afford exclusively the trans-products. To account for our findings, the following mechanistic model involving a catalytic iodonium intermediate was proposed to account for both the stereoretention (Scheme [6b], pathway a) and stereoerosion (Scheme [6b], pathways b, c, and d). To address the presence of the proposed iodenium intermediate, we pre-synthesized the iodoselectfluor reagent D (Scheme [4a]). Substituting this reagent in place of the catalyst combination, we observed nearly identical yields and regioselectivity of the desired product, suggesting that it is likely a key intermediate in the reaction.
# 5
Future Outlook
Our work here represents a rare example of the catalytic use of iodonium for regioselective alkene difunctionalization. While tremendous progress has recently been made in regioselective alkene difunctionalizations, regiodivergent coupling reactions of π-components remain relatively unexplored.[25] Processes that can effectively control access to both regiochemical outcomes with exceptional selectivity remain an exceptional challenge.[13p] , [14`] [b] [c] [d] , [26] A parallel illustration of the importance and difficulty in the development of regiodivergent processes can be found in alkene hydrofunctionalizations. While the Markovnikov’s rule to predict and guide alkene hydrofunctionalization reactions was discovered as early as 1869, catalytic strategies to access the anti-Markovnikov products remained as one of ‘the top 10 challenges in catalysis’ until very recently.[27] An interesting direction that our group is currently venturing is the utilization of halonium as both a catalytic and regiocontrol template to design regiodivergent alkene difunctionalization reactions. For example, can we simply control the nucleophilicity of the bifunctional reagent to control the regiodetermining step? What is the role of the halonium in the regiochemical control process? How do we design catalytic solutions to develop regiodivergent processes for more challenging olefin substrates or carbon-based bifunctional nucleophiles? Furthermore, the development of regiodivergent and enantioselective protocols clearly represents an area of significant interest and exceptional challenge to the synthetic community (Scheme [7]). For a historically important and valuable synthetic intermediate, haloniums have for a large extent been left in many chemists’ hindsight. We believe that our work, and perhaps along with others, will prove such views of haloniums to be unjustified.
#
#
Acknowledgment
We thank Dr. Yong W. Kim (University of Toledo) for NMR assistance.
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References and Notes
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Current addresses:
For a selected recent review, see:
For selected recent examples, see:
For selected reviews on halofunctionalization and halogenation, see:
For selected examples on halocyclization processes, see:
A very interesting early example using bromine catalysis was also demonstrated by Sharpless, see:
For selected stoichiometric examples, see:
For selected reviews on olefin difunctionalizations, see:
For selected recent examples on olefin difunctionalizations, see:
For selected examples of osmium-catalyzed strategies, see:
For selected intramolecular examples based on palladium-catalysis, see:
For selected recent reviews and examples based on copper catalysis, see:
For a selected example of Ir-catalyzed strategies, see:
For selected examples based on other metal-catalyzed strategies, see:
For selected examples of metal-free strategies, see:
For selected examples of intermolecular alkene oxyamination strategies, see:
For selected reviews and examples of using directing groups in alkene difunctionalizations, see:
For other selected synthetic examples for this class of heterocycles, see:
For selected examples of regiodivergent couplings, see:
Corresponding Author
Publication History
Received: 15 September 2020
Accepted after revision: 02 October 2020
Accepted Manuscript online:
02 October 2020
Article published online:
16 November 2020
© 2020. Thieme. All rights reserved
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References and Notes
- 1a Eric Cheng, Miami University, Oxford, OH, USA. E-Mail: chengeh@miamioh.edu
- 1b Fan Wu, Ningbo University, P. R. of China. E-mail: wufan@nbu.edu.cn.
- 2 Roberts I, Kimball GE. J. Am. Chem. Soc. 1937; 59: 947
- 3a Olah GA, Bollinger JM. J. Am. Chem. Soc. 1967; 89: 4744
- 3b Olah GA, Schilling P, Westerman PW, Lin HC. J. Am. Chem. Soc. 1974; 96: 3581
- 3c Wieringa JH, Strating J, Wyndberg H. Tetrahedron Lett. 1970; 11: 4579
- 3d Brown RS, Nagorski RW, Bennet AJ, McClung RE. D, Aarts GH. M, Klobukowski M, McDonald R, Santarsiero BD. J. Am. Chem. Soc. 1994; 116: 2448
- 3e Mori T, Rathore R, Lindeman SV, Kochi JK. Chem. Commun. 1998; 927
- 3f Nugent WA. J. Org. Chem. 1980; 45: 4533
- 4a Brown RS. J. Acc. Chem. Res. 1997; 30: 131
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Current addresses:
For a selected recent review, see:
For selected recent examples, see:
For selected reviews on halofunctionalization and halogenation, see:
For selected examples on halocyclization processes, see:
A very interesting early example using bromine catalysis was also demonstrated by Sharpless, see:
For selected stoichiometric examples, see:
For selected reviews on olefin difunctionalizations, see:
For selected recent examples on olefin difunctionalizations, see:
For selected examples of osmium-catalyzed strategies, see:
For selected intramolecular examples based on palladium-catalysis, see:
For selected recent reviews and examples based on copper catalysis, see:
For a selected example of Ir-catalyzed strategies, see:
For selected examples based on other metal-catalyzed strategies, see:
For selected examples of metal-free strategies, see:
For selected examples of intermolecular alkene oxyamination strategies, see:
For selected reviews and examples of using directing groups in alkene difunctionalizations, see:
For other selected synthetic examples for this class of heterocycles, see:
For selected examples of regiodivergent couplings, see:
Alexander K. Vogel is a native of Toledo and a current senior undergraduate student at the University of Toledo. His research work focuses on the synthesis of firefly luciferin analogues to examine their photochemical properties.
Elizabeth C. Ziegelmeyer is a junior undergraduate student at the University of Toledo. Her current research focuses on the catalytic utilization of iodonium intermediates.
Eric Cheng is a sophomore undergraduate student at Miami University (OH). He conducted research on alkene difunctionalizations in the research group during the summer of 2019.
Fan Wu obtained his PhD from the University of Toledo studying alkene difunctionalization methods for heterocycle synthesis. He is currently a research faculty at Ningbo University, where his research work focuses on the development of late-stage functionalization strategies on bioactive molecules and natural products.
Leo P. Roberts is a sophomore undergraduate student at the University of Toledo, where his research focuses on the synthesis of firefly luciferin analogues.
Megan M. Vesoulis is a freshman undergraduate student at the University of Toledo. Her research involves the catalytic utilization of iodonium intermediates.
Wei Li obtained his PhD (Prof. John Montgomery) at the University of Michigan studying nickel-catalyzed coupling reactions. Following his postdoctoral studies (Prof. David W. C. MacMillan) at Princeton University on C–N bond formations and photoredox catalysis, he began his independent career at the University of Toledo in 2015, where his group is dedicated to the discovery and development of new catalytic avenues to facilitate access to pharmaceuticals.