Letter Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Synthesis of Sultams and Cyclic N‑Sulfonyl Ketimines via IronCatalyzed Intramolecular Aliphatic C−H Amidation Dayou Zhong,† Di Wu,† Yan Zhang,† Zhiwu Lu,† Muhammad Usman,† Wei Liu,† Xiuqiang Lu,‡ and Wen-Bo Liu*,†,§ †
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Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, China ‡ Fuqing Branch of Fujian Normal University, Fuzhou 350300, Fujian, China § Sauvage Center for Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China S Supporting Information *
ABSTRACT: Cyclic sulfonamides (sultams) play a unique role in drug discovery and synthetic chemistry. A direct synthesis of sultams by an intramolecular C(sp3)−H amidation reaction using an iron complex in situ derived from Fe(ClO4)2 and aminopyridine ligand is reported. This strategy features a readily available catalyst and tolerates a broad variety of substrates as demonstrated by 22 examples (up to 89% yield). A one-pot iron-catalyzed amidation/ oxidation procedure for the synthesis of cyclic N-sulfonyl ketimines is also realized with up to 92% yield (eight examples). The synthetic utility of the method is validated by a gram-scale reaction and derivatization of the products to ring-fused sultams.
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established utilizing both precious metals (i.e., Rh,7a−c Ru,7d,e Ir,7f,g Ag7h) and base metals (i.e., Fe,8 Co,9a−c Cu,9d,e Mn9f−h) as the catalysts. However, such a strategy in the synthesis of sultams has thus far not been explored, and there are only a handful of examples known to date.5,6 Pioneering work by Dawson and Breslow,5a and more recently by the Arnold,5b,c Fasan,5d,e and Hartwig5f groups, resulted in successful construction of benzosultams by intramolecular enzymatic C−H aminations with arylsulfonyl azides (Scheme 1a). The impressive works by Zhang6a and Katsuki6b uncovered that Co−porphyrin and Ir−salen complexes are able to catalyze the cyclization of sulfonyl azides, respectively (Scheme 1b). Although those examples represent powerful methods, the substrates are limited to arylsulfonyl azides, and therefore, only benzosultams are provided. A more synthetically useful route to the sultams that uses readily available catalysts and operates with good substrate scope is thus highly desirable. Recently, we have reported that a simple iron/aminopyridine catalytic system enables the selective amidation of aliphatic C−H bonds of sulfamate esters with high reactivity.11 We expected that the iron complexes would serve as catalysts for the straightforward synthesis of sultams by the iron−nitrenoid C−H bond insertion of linear aliphatic sulfonamides (Scheme 1c). It is of particular interest that those aliphatic sultams can be easily alkylated at the N-atom to afford a library of sultam derivatives. Moreover, a feasible method for the synthesis of cyclic N-
ulfonamides have been widely recognized as an important class of structures in pharmaceuticals and agrochemicals due to their broad spectrum of bioactivities.1,2 In particular, cyclic sulfonamides (sultams) are often incorporated into the target molecules as a stable lactam equivalent and, thus, have gained increasing popularity in medicinal chemistry (Figure 1).2 Additionally, sultams have been widely utilized with
Figure 1. Representative examples of bioactive sultams.
success in the construction of heterocycles and natural products.3 Consequently, there have been a variety of strategies developed for the synthesis of sultams,4 such as Diels−Alder cyclization,4c ring-closing metathesis,4d−f radical cyclization,4g intramolecular Heck reaction,4h and most recently, metal−nitrenoid C−H insertions.5,6 The last decades have seen the notable progress in the formation of C−N bonds via metal−nitrenoid C−H insertion reactions.7−10 A number of efficient methods have been © XXXX American Chemical Society
Received: May 16, 2019
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DOI: 10.1021/acs.orglett.9b01732 Org. Lett. XXXX, XXX, XXX−XXX
Letter
Organic Letters
Gratifyingly, we observed that 1a could be transformed into the desired sultam 2a smoothly using 10 mol % of Fe(ClO4)2/ L1 as the catalyst and PhI(OAc)2 as the oxidant in MeCN at 80 °C (entry 1). Cyclic ketimine 3a was also observed as a minor byproduct (2a:3a = 4.9:1). Other oxidants were examined (entries 2−4), and PhI(OPiv)2 provided better results in terms of yield and 2a:3a ratio (entry 3). Screening of ligand effects (entries 5−10) revealed that L2 was able to slightly improve the reactivity of the reaction, and 2a was isolated in 81% yield (entry 5). Lowering the reaction temperature to 60 °C resulted in a diminished yield and a lower 2a:3a ratio (entry 11). No desired product was formed in the absence of either the ligand or Fe(ClO4)2 (entries 12 and 13). Thus, we have identified the optimal reaction conditions as described in entry 5 of Table 1. Naturally, the substrate scope was examined next as summarized in Scheme 2. Substrates containing both
Scheme 1. Synthetic Approaches to Sultams by Direct C−H Amidations
Scheme 2. Substrate Scope for the Sultam Synthesisa sulfonyl ketimines, 12 which are useful precursors for enantioselective construction of sultams,13 is also developed here via the direct C−H amidation followed by oxidation with PhI(OCOCF3)2 (PIFA) in one-pot. We looked into the iron−nitrenoid C(sp3)−H insertion reaction with 3-phenylpropane-1-sulfonamide 1a as a model substrate. The condition optimizations, including the investigations of the oxidants (Table S1), solvents (Table S2), iron precursors (Table S3), and ligands (Table S4), were carried out, and the selected results are summarized in Table 1. Table 1. Condition Optimizations
entrya 1 2 3 4 5 6 7 8 9 10 11e 12f 13g
ligand (x mol %) L1 L1 L1 L1 L2 L3 L4 L5 L6 L7 L2 − L2
(20) (20) (20) (20) (20) (20) (20) (20) (30) (30) (20) (20)
oxidant
yieldb (%)
2a/3ab
1ac (%)
PhI(OAc)2 PIFA PhI(OPiv)2 PhI(DMM) PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2 PhI(OPiv)2
82 32 83 (73)d 63 90 (81)d 47 25 75 83 84 79 − −
4.9:1 1:>20 8.2:1 6:1 8:1 >20:1 >20:1 3.7:1 3.4:1 3:1 4.6:1 − −
− 53 − − − 41 53 6 − − − 71 83
a
Reaction conducted on a 0.2 mmol scale under the conditions of entry 5, Table 1. Yields are of isolated 2, and the values in parentheses are isolated yields of 3. bNot observed. cWith 2.5 equiv of PhI(DMM) instead of PhI(OPiv)2. dWith 30 mol % of L6 instead of L2. eWith 20 mol % of L1 instead of L2.
electron-rich and electron-deficient groups (Me, MeO, Cl, Br, CF3, and NO2) on the para-position of the aryl ring produced the desired γ-sultams 2b−2g in 52−88% yields along with the corresponding overoxidized N-sulfonyl ketimines 3b− 3g in fairly small amounts (6−23%). Substituents on the orthoand meta-positions of the aryl group were also tolerated, giving the resultant products 2h−2m in 61−89% yields. Intramolecular cyclization of sulfonylamide 1n proceeded smoothly to exclusively give δ-sultam 2n in 70% yield. Notably, a TMSethynyl-substituted sultam 2p was produced as well in 53% yield. Arylsulfonamides 1o and 1p were applicable to the present C−H insertion chemistry under slightly modified conditions (with PhI(DMM) as the oxidant). Consequently, benzosultams 2o and 2p were obtained in moderate yields. Whereas the iron−nitrenoid insertion of aliphatic C(sp3)−H
a
Reaction conditions: 1a (0.1 mmol), Fe(ClO4)2 (10 mol %), PhI(OPiv)2 (0.2 mmol), 4 Å MS, MeCN (1.0 mL), 80 °C. b Combined yield of 2a and 3a as determined by 1H NMR using 1,3,5-trimethoxybenzene as an internal standard. cRemaining 1a as determined by 1H NMR. dIsolated yield of 2a. e60 °C. fWithout ligand. gWithout Fe(ClO4)2. PIFA = PhI(OCOCF3)2. PhI(DMM) = phenyliodonium dimethylmalonate. B
DOI: 10.1021/acs.orglett.9b01732 Org. Lett. XXXX, XXX, XXX−XXX
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Organic Letters
Scheme 3. Substrate Scope for the Synthesis of Cyclic NSulfonyl Ketiminesa
bond is challenging,8,10g,h,11 our catalytic system was shown to enable the reaction of such inert substrates (2r−2t). The reactions of tertiary (1r) and secondary (1s) C(sp3)−H bonds delivered sultams 2r and 2s in 68% and 74% yields, respectively. Remarkably, regioselective C−H amidation of octane-1-sulfonamide 1t was achieved to form five- or sixmembered sultams (2t and 2t′) upon the judicious choice of ligands. When L6 was used, the γ-sultam 2t was obtained as the major product (75% yield, 2t:2t′ = 2:1). By screening the conditions (Table S5), the δ-sultam 2t′ was provided dominantly with L1. For olefin-containing substrate 1u, allylic C−H amination was observed as the major pathway to form 2u together with the formation of aziridination product 2u′.14 The ester group was also tolerated to form sultam 2v in 54% yield. Additional comments regarding to the substrate scope are noteworthy. First, for aryl sulfonamides 1o and 1p, the use of Chen’s PhI(DMM) reagent15 is critical to the reactivity. In contrast, low reactivities were observed with PhI(OPiv)2 as the oxidant for those substrates. Second, for the examples that delivered sultams through unactivated C(sp3)−H insertions (not benzylic or propargylic C−H bonds, i.e., substrates 2r− 2t), PhI(DMM) was also found to be superior to PhI(OPiv)2, resulting in increased yields of the cyclization products. Third, although the formation of overoxidized byproducts 3 can not be avoided in the reactions for many substrates, those Nsulfonyl imines were usually produced in small portions (around 10% in most cases) and can be readily removed by column chromatography. Cyclic N-sulfonyl ketimines 3 are useful synthons in stereoselective transformations,13 which are normally synthesized through multiple steps involving ring-opening of epoxide with protected methanesulfonamide under cryogenic conditions, oxidation of the resultant alcohol to ketone, deprotection, and condensation to form the imine.12c A convenient synthetic method for those substances would be f useful and important. During condition optimizations, we noticed that the formation of imine 3a is related to the choice of hypervalent iodine(III) reagents16 (Table 1). When PIFA was used as an oxidant, only the ketimine 3a was observed in 32% yield together with 53% recovered starting material 1a (entry 2, Table 1). This result indicates that the oxidation of the sultam 2a to the imine 3a by PIFA is much faster than the iron−nitrenoid insertion of 1a. Encouraged by this finding, a one-pot synthesis of the cyclic N-sulfonyl ketimines 3 was developed through the iron-catalyzed C−H amidation followed by the oxidation of sultams with 1.2 equiv of PIFA (Scheme 3). The transformation of the standard substrate 1a provided cyclic imine 3a in 88% yield. A quick survey including various aryl-substituted propane-1-sulfonamides all led to the formation of the corresponding cyclic ketimines (3c, 3d, 3f− 3j) in 75−92% yields. After the development of the efficient directed C−H amidation reaction, the scalability and further transformations of the resulting sultams and ketimines were also explored (Scheme 4). First, the reaction was carried out on an 8.0 mmol scale to provide the sultam 2a in 72% yield together with only 5% yield of 3a. A sequential N-allylation and α-allylation of sulfonamide 2a followed by a ring-closing metathesis (RCM) reaction produced a [4.2.1]-bridged bicyclic sultam 4 in 55% overall yield. Furthermore, ketimine 3a was readily converted into a [6.5]-fused bicyclic sultam 5 in 75% yield via a sequence involving a nucleophilic addition of allylMgBr to the imine, Nallylation, and an RCM reaction.
a
Reactions conducted under the standard conditions of Scheme 2 for 2 h followed by the addition of PIFA (1.2 equiv) for another 1 h; see the SI for details.
Scheme 4. Scale-up Reaction and Product Transformations.a
a
Conditions: (a) (i) allyl bromide, K2CO3, acetone, reflux, 8 h; (ii) nBuLi, allyl bromide, THF, −78 °C, 2 h, 70% yield of two steps; (iii) Hoveyda−Grubbs-II (HG-II, 5 mol %), CH2Cl2, reflux, 12 h, 78% yield; (b) (i) allylMgBr, THF, −15 °C, 6 h; (ii) allyl bromide, K2CO3, acetone, reflux, 24 h, 83% yield of two steps; (iii) HG-II (5 mol %), CH2Cl2, rt, 1 h, 90% yield. See the SI for details.
In conclusion, we have uncovered an efficient method for the synthesis of sultams and cyclic N-sulfonyl ketimines. The iron complexes derived from Fe(ClO4)2 and aminopyridine ligands furnish the sultams in good yields from aliphatic sulfonamides. The substrate scope of this iron−nitrenoid insertion covers both benzylic and aliphatic C−H bonds. A one-pot C−H amidation and oxidation procedure has also been developed to construct cyclic N-sulfonyl ketimines. We anticipate that the simple and readily available catalysts and the high reactivity toward aliphatic substrates of this method will not only allow efficient access to sultam derivatives but also open new avenues for their exploration in drug discovery.
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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.9b01732. Additional data and experimental details, including Tables S1−S5; characterization data and spectra of all new compounds (PDF) C
DOI: 10.1021/acs.orglett.9b01732 Org. Lett. XXXX, XXX, XXX−XXX
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Wen-Bo Liu: 0000-0003-2687-557X Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We gratefully acknowledge the NSFC (21772148, 21602160), the Fundamental Research Funds for the Central Universities (2042018kf0017), the National Program for 1000 Young Talents of China, and Wuhan University (WHU) for financial support.
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REFERENCES
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DOI: 10.1021/acs.orglett.9b01732 Org. Lett. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.orglett.9b01732 Org. Lett. XXXX, XXX, XXX−XXX
