Iron(MCP) Complexes Catalyze Aziridination with Olefins As Limiting Reagents

Article abstract of DOI:10.1021/acs.joc.8b00402

Herein described are the first efficient nitrogen-atom transfer reactions mediated by iron N,N′-dimethyl-N,N′-bis(2-pyridinylmethyl)cyclohexane-1,2-diamine- (MCP-) and 2-({1-[(pyridin-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-yl}methyl)pyridine-type (PDP-type) complexes. These catalysts affect styrene aziridination under mild conditions based on a limiting quantity of olefin substrate.

Full text of DOI:10.1021/acs.joc.8b00402

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Iron(MCP) Complexes Catalyze Aziridination with Olefins as Limiting Reagents
Mina F. Shehata, Suraj K. Ayer, and Jennifer L. Roizen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00402 • Publication Date (Web): 12 Apr 2018
Downloaded from http://pubs.acs.org on April 12, 2018
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Iron(MCP) Complexes Catalyze Aziridination with Olefins as Limiting
Reagents
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Mina F. Shehata,† Suraj K. Ayer,† and Jennifer L. Roizen*
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Duke University, Department of Chemistry, Box 90346, Durham, North Carolina 27708–0354,
USA
Supporting Information Placeholder
ABSTRACT: Herein described are the first efficient nitrogenꢀatom transfer reactions mediated
by iron N,N’ꢀdimethylꢀN,N’ꢀbis(2ꢀpyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamineꢀ (MCPꢀ) and 2ꢀ({1ꢀ
[(pyridinꢀ2ꢀylmethyl)pyrrolidinꢀ2ꢀyl]pyrrolidinꢀ1ꢀyl}methyl)pyridineꢀtype
(PDPꢀtype)
complexes. These catalysts affect styrene aziridination under mild conditions based on a limiting
quantity of olefin substrate.
INTRODUCTION
Molecular nonꢀheme iron complexes catalyze remarkable processes, transforming aliphatic
hydrocarbons through hydroxylation1 or dehydrogenation,2 and olefins through dihydroxylation
or epoxidation (Scheme 1).3 For these oxygenꢀtransfer reactions, many of the most synthetically
Scheme 1. Non-heme iron complexes mediate alkene oxidation
versatile and siteꢀselective iron catalysts are based on MCPꢀ4 (1a–1i) and PDPꢀtype5 ligands (1j–
1m, Tables 1–2). By comparison, fewer nonꢀheme iron complexes are known to advance
7,
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nitrogenꢀtransfer reactions.6,
Indeed, to our knowledge, neither MCPꢀ nor PDPꢀtype
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complexes have been developed in nitrogenꢀtransfer processes. We hypothesized that MCPꢀ and
PDPꢀtype iron complexes would affect efficient nitrogenꢀtransfer, and that the qualitative
reactivity trends for known oxygenꢀtransfer processes would have predictive value for the
developed nitrogenꢀtransfer process. To evaluate these hypotheses, MCPꢀ and PDPꢀtype iron
complexes have been employed to affect aziridination. While aziridination reactions benefit from
the use of a substrate with polarizable and electronically accessible πꢀorbitals to trap the
nitrogenꢀcentered oxidant, even the most synthetically promising nonꢀheme iron catalysts with
two available coordination sites require an excess of alkene to produce racemic aziridines.9
Herein described is a mild aziridination reaction that employs a limiting quantity of olefin
substrate. This system is used to establish a qualitative relationship between reaction efficiency
and MCPꢀ and PDPꢀtype catalyst architecture.
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RESULTS AND DISCUSSION
Anticipating that the efficiency of nitrogenꢀatom transfer process would rely on catalyst
architecture, we chose to focus on 2ꢀpyridinylmethyl substitution of the ligand and ligand
variations designed to sterically shield the iron center. To investigate the effect of 2ꢀ
pyridinylmethyl substitution on this nitrogenꢀtransfer process, novel Fe(MCP) complexes 1a–1f
have been prepared (Table 1). Throughout this manuscript, the molecular formulas of new metal
complexes have been confirmed by elemental analysis. Absent data to confirm connectivity,
these complexes are depicted in their acetonitrile solvated forms. MCPꢀtype complexes 1a–1f
could adopt cisꢀα or cisꢀβ topology.10 Closely related Mn4b, 11a–c and Fe4c, 11d complexes are C2ꢀ
symmetric with ligands that adopt a cisꢀα topology.
These MCPꢀtype complexes affect nitrogenꢀtransfer to convert olefin 2a to nosyl12 aziridine13,14
3a using [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodane (PhINNs, 4a)15 as a nitrogen source
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(Table 1). Other aryl sulfonamides16 can serve as nitrogenꢀtransfer precursors to generate
aziridine 3b and 3c, albeit in slightly diminished yields. In these aziridination processes, the
counterion in the preꢀcatalyst impacts reactivity with the most effective complexes incorporating
weakly coordinating triflate or perchlorate ions, or nonꢀcoordinating hexafluoroantimonate ions,
rather than strongly coordinating chloride ions.
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Table 1. Counteranion influences aziridination efficiency; Ligand 2-pyridinylmethyl
substitution has limited impact
aGeneral reaction conditions: 1.0 equiv alkene 2a, 1.5 equiv PhINR (4), 5 mol % [Fe] complex 1,
b
c
0.167 M CH3CN, 21 °C. Isolated yield. All complexes provide aziridine 3a as a 1:1 ratio of
d
enantiomers as determined by chiral HPLC. Metal complexes have been prepared using
e
enantiomerically enriched ligands (see Supporting Information). Complex prepared by General
Procedure A. fComplex prepared by General Procedure B.
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Despite the beneficial effect of 2ꢀpyridinylmethylꢀsubstituted ligands on some oxygenꢀtransfer
reactions,11 in this nitrogenꢀtransfer process, differential 2ꢀpyridinylmethyl substitution has an
insignificant effect on reaction efficiency and enantioinduction. Critically, MCPꢀligation of iron
improves reaction efficiency,17 as Fe(OTf)2 and Fe(ClO4)2•6H2O furnish aziridine 3a in reduced
yields (see Supporting Information). We chose to employ perchlorate complexes in subsequent
investigations, noting the higher background conversion with Fe(OTf)2 relative to
Fe(ClO4)2•6H2O.
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In reactions mediated by complex 1a, alkene 2a is not fully consumed, presumably due to
catalyst arrest. One catalyst arrest pathway involves oxidative Nꢀdealkylation of the ligand in
complex 1a to give ketone 5a (Scheme 2). A similar process is known under oxygenꢀtransfer
conditions.17
Scheme 2. Oxidative N-dealkylation of the ligand proceeds under reaction conditions
To further investigate the role of catalyst architecture in nitrogenꢀtransfer processes, iron
complexes have been prepared with sterically varied Lꢀtype donors (Table 2). Based on
similarity to known metal complexes,18–21 these ligands are expected to generate C1ꢀ or C2ꢀ
symmetric metal complexes 1g–1n.
In the aziridination of alkene 2a, 5ꢀpyridylꢀsubstituted Fe(MCP) perchlorate 1g and triflate 1h
outperform unsubstituted Fe(MCP) complex 1f and Fe(PDP)ꢀtype complexes 1j–1m as catalysts
(Table 2). Under optimal conditions, olefin 2a reacts with PhINNs (4a) to furnish aziridine 3a in
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71% yield at room temperature with 1g as a catalyst (Table 2). Under the same conditions,
triflate 1h displays similar catalytic efficacy.
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In practical terms, aziridination methods22 are synthetically important: aziridines are potent
pharmacophores,23 ligands for catalysis,24 and versatile precursors to bioactive fine chemicals
and materials.25 Nosyl aziridines offer more limited utility as activated electrophiles,13 and are
readily accessible using the developed method. Under the optimized conditions,26 limiting
quantities of electronically varied styrenes react with moderate efficiency to generate racemic
aziridines (Table 3, entries 1–9, 14–15). The reaction tolerates a pendant acetate, bromine atom,
nitrile, MIDA boronate ester, phenolic ether and ketone (entries 2, 5–10). These conditions
enable aziridination of challenging substrates, such as 3ꢀvinylestrone27 and Lewis basic 2ꢀ
vinylpyridine (entries 10–11). These conditions are less effective with unconjugated 1ꢀoctene,
and convert 1ꢀphenylpropꢀ2ꢀenꢀ1ꢀone in modest yields (entries 12–13). Moreover, aziridination
of isomerically pure cisꢀ1ꢀphenylꢀ1ꢀpropene proceeds with erosion of the original olefin
geometry (Table 3, entry 14).
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Table 2. Effect of 5-pyridyl-substituted MCP-type and PDP-type ligands on aziridination
reactions
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aGeneral reaction conditions: 1.0 equiv alkene 2a, 1.5 equiv PhINR (4), 5 mol % [Fe] complex 1,
b
c
0.167 M CH3CN, 3 h, 21 °C. Isolated yield. Complex prepared by General Procedure A. 1.5 h
run time. dComplex prepared by General Procedure B. 1.5 h run time.
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Table 3. A general protocol to aziridinate olefins
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aGeneral reaction conditions: 1.0 equiv alkene 2, 1.5 equiv PhINNs (4a), 5 mol % [Fe] complex
b
c
1g, 0.167 M CH3CN, 21 °C. Isolated yield. Isolated as a 91:9 mixture of syn/anti isomers.
Analysis of recovered cisꢀ1ꢀphenylpropene from the reaction revealed partial isomerization in
the alkene to give a 78:22 ratio cis/transꢀ1ꢀphenylpropene.
Other nonꢀheme iron complexes engage reactive nitrogen species to affect addition of a
nitrogenꢀcentered radical across an olefin, or singleꢀelectron transfer (SET) pathways (Scheme
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2).7b, 7e, 7g, 29 To indirectly probe the ability of the active oxidant to affect SET under the reaction
conditions, we carried out dimerization experiments. SET has been observed in a related system
in which an isolable Fe(IV)ꢀtosylimido acts as a oneꢀelectron oxidant to promote N,Nꢀ
dimethylaniline dimerization.29 Indeed, under the conditions developed herein, selective
dimerization of electronꢀrich aniline 6 suggests that the active oxidant can induce SET from
more electronꢀrich substrates (Scheme 3). By contrast, the active oxidant does not induce
dimerization of less oxidatively labile30 benzonitrile (8), which suggests that SET may not be
feasible for less oxidatively labile substrates.
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Scheme 3. The active oxidant affects SET from an arene
CONCLUSION
In conclusion, we have realized an efficient nitrogenꢀtransfer reaction catalyzed by Fe(MCP)ꢀ
and Fe(PDP)ꢀtype complexes. Reaction efficiency is minimally influenced by 2ꢀpyridinylmethyl
substitution of the ligand; however, ligand variations that are designed to sterically shield the
iron center increase reaction turnover. This aziridination reaction proceeds under mild conditions
and does not require the use of excess olefin. Conceptually, nitrogenꢀtransfer technologies
mediated by nonꢀheme iron complexes could provide insight into differential reactivity of
oxygenꢀ and nitrogenꢀtransfer intermediates. Consequently, we anticipate that this investigation
will enable further research to elucidate reactivity differences between ironꢀmediated oxygenꢀ
and nitrogenꢀatom transfer processes.
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EXPERIMENTAL
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General Information. Moistureꢀsensitive reactions were performed using flameꢀdried glassware
under an atmosphere of dry nitrogen (N2). Airꢀ and waterꢀsensitive reactions, where noted, were
performed in an MBraun MB200 glovebox held under an atmosphere of nitrogen gas (working
pressure 2–6 mbar). Flameꢀdried equipment was stored in a 130 °C oven before use and either
allowed to cool in a cabinet dessicator or assembled hot and allowed to cool under an inert
atmosphere. Airꢀ and moistureꢀsensitive liquids and solutions were transferred via plastic or
glass syringe. Chromatographic purification of products was accomplished using Teledyne Isco
CombiFlashRf system using 12–220 g Redi Sep Rf normal phase silica columns (particle size
40–63 µm irregular, 230–400 mesh). Thin layer chromatography was performed on EMD
Millipore silica gel 60 F254 glassꢀbacked plates (layer thickness 250 µm, particle size 10–12 ꢁm,
impregnated with a fluorescent indicator). Visualization of the developed chromatogram was
accomplished by fluorescence quenching under shortwave UV light and/or by staining with pꢀ
anisaldehyde or KMnO4 stains. NMR spectra were obtained on Varian iNOVA spectrometers
operating at 400 or 500 MHz for 1H NMR, 101 or 126 MHz for 13C NMR, and 376 MHz for 19F
NMR at 23–25 °C, and are reported as chemical shifts (δ) in parts per million (ppm). Spectra
were referenced internally according to residual solvent signals (1H: CDCl3, 7.26 ppm; 13C:
CDCl3, 77.0 ppm; acetoneꢀd6, 29.2). Data for NMR spectra use the following abbreviations to
describe multiplicity: s, singlet; br s, broad singlet; d, doublet; t, triplet; q, quartet; dd, doublet of
doublet; td, triple of doublet; ddd, doublet of doublet of doublets; ddt, doublet of doublet of
triplets; app dd, apparent doublet of doublets; ABq, AB system quartet; m, multiplet. Coupling
constant (J) are reported in units of Hertz (Hz). IR spectra were obtained on a Nicolet 6700 FTꢀ
IR system. Peaks are reported in cm–1 with indicated relative intensities: s (strong, 0–33% T); m
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(medium, 34–66% T); w (weak, 67–100% T); and br (broad). High resolution mass spectra
(HRMS, m/z) were recorded on an Agilent LCMSꢀTOFꢀDART spectrometer using electrospray
ionization (ESI, Duke University Department of Chemistry Instrumentation Center).
Enantiomeric ratios were determined by HPLC PhenomenexTM Lux® Cellulose I in comparison
with authentic racemic materials on a Shimadzu Prominence Modular HPLC. All reagents
obtained from commercial suppliers were used a received.
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Preparation and Characterization of Ligand. The ligand was prepared according to a
modified literature procedure.31
5ꢀ(3,5ꢀbis(trifluoromethyl)phenyl)ꢀ2ꢀ(chloromethyl)pyridine (10a). A flameꢀdried 50 mL round
bottom flask charged with a stir bar was transferred to a nitrogenꢀfilled glovebox where
Pd(OAc)2 (74.8 mg, 0.33 mmol, 3 mol%), SPhos (275.1 mg, 0.67 mmol, 6 mol%), 3,5ꢀ
bis(trifluoromethyl)bromobenzene (3.25 g, 11.1 mmol, 1.0 equiv), and K3PO4 (4.71 g, 22.2
mmol, 2.0 equiv) were added to the flask. The flask was equipped with a reflux condenser,
sealed with a Teflon septum, and removed from the glovebox. Toluene (20 mL) and degassed
deionized water (2 mL) were added to the flask via syringe followed by 2ꢀ(((tertꢀ
butyldimethylsilyl)oxy)methyl)ꢀ5ꢀ(4,4,5,5ꢀtetramethylꢀ1,3,2ꢀdioxabotolanꢀ2ꢀyl)pyridine (5.82 g,
16.6 mmol, 1.5 equiv). The reaction was heated at 100 °C in an oil bath for 16 h, at which time it
was allowed to cool to room temperature for 30 min and quenched with water (10 mL). The
layers were separated and the aqueous layer was extracted with CH2Cl2 (3 x 10 mL). The
combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced
pressure. The crude solid was dissolved in ethanol (15 mL) and 3N HCl (12 mL). The reaction
was vigorously stirred for 3 h, quenched to neutral pH with saturated NaHCO3, and diluted with
CH2Cl2 (30 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2 (3
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x 20 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under
reduced pressure to obtain a crude solid. The solid was dissolved in CH2Cl2 (50 mL) and SOCl2
(8.2 mL, 13.2 g, 111 mmol, 10 equiv) was added dropwise via airtight syringe. The reaction was
stirred for 12 h and quenched to neutral pH with saturated NaHCO3. The layers were separated
and the aqueous layer was extracted with CH2Cl2 (3 x 20 mL). The combined organic layers were
dried over Na2SO4, filtered, and concentrated under reduced pressure to obtain a yellow solid.
The yellow solid was purified via silica gel column chromatography using hexanes:EtOAc (95:5)
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1
to obtain the desired product as a white solid (2.18 g, 58% yield). H NMR (400 MHz, CDCl3) δ
8.82 (d, J = 2.4 Hz, 1H), 8.00 (br s, 2H), 7.97 (d, J = 2.4 Hz, 1H), 7.94–7.91 (m, 1H), 7.64 (d, J =
8.1 Hz, 1H), 4.75 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 157.2, 147.7, 139.5, 135.7, 133.3,
19
132.6 (q, J = 33.7 Hz), 127.3, 123.0, 123.2 (q, J = 272.8 Hz), 122.0, 46.2; F NMR (376 MHz,
CDCl3) δ –62.98; IR (neat) ν 3099 (w), 3023 (w), 2968 (w), 773 (m), 717 (s) cmꢀ1; TLC Rf =
0.62 (hexanes:EtOAc 7:3); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C14H9ClF6N 340.0322;
Found 340.0327.
(2R,
2′R)ꢀ1,1′ꢀbis((5ꢀ(3,5ꢀbis(trifluoromethyl)phenyl)pyridineꢀ2ꢀyl)methyl)ꢀ2,2′ꢀbipyrrolidine
(10b). A flameꢀdried 50 mL round bottom flask was charged with a stir bar, 5ꢀ(3,5ꢀ
bis(trifluoromethyl)phenyl)ꢀ2ꢀ(chloromethyl)pyridine (10a, 0.94 g, 2.75 mmol, 2.2 equiv), (R,
R)ꢀ2,2′ꢀbispyrrolidine/Lꢀtartaric acid (363 mg, 1.25 mmol, 1.0 equiv), NaOH (320 mg, 8 mmol,
6.4 equiv), and 1:1 CH2Cl2:H2O (10 mL) and the reaction was stirred vigorously at room
temperature for 12 h. The reaction was then diluted with 1 M NaOH and CH2Cl2 (10 mL). The
layers were separated and the aqueous layer was extracted with CH2Cl2 (5 x 5 mL). The
combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced
pressure to orangeꢀyellow solid. The solid was purified via silica gel column chromatography
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using hexanes:EtOAc (7:3), to obtain the desired product as a white powder (0.45 g, 53% yield).
1H NMR (400 MHz, CDCl3) δ 8.71 (d, J = 2.5 Hz, 1H), 7.93 (s, 2H), 7.88 (s, 1H), 7.81 (dd, J =
8.1, 2.5 Hz, 1H), 7.56 (d, J = 8.1 Hz, 1H), 3.99 (ABq, J = 15.0 Hz, ꢀν = 283.4 Hz, 4H), 3.13–
3.00 (m, 1H), 2.90–2.87 (m, 2H), 2.29 (q, J = 8.2 Hz, 2H), 1.89 (s, 1H), 1.86 – 1.70 (m, 9H),
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1.61 (s, 3H); C NMR (126 MHz, CDCl3) δ 161.4, 147.0, 140.1, 134.9, 132.5 (q, J = 32.6 Hz),
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131.8, 127.0, 124.2, 123.2 (q J = 273.2 Hz), 121.5, 66.2, 61.0, 55.4, 26.5, 23.7; F NMR (376
MHz, CDCl3) δ –63.01; IR (neat) ν 2959 (s), 717 (m) cmꢀ1; TLC Rf = 0.25 (hexanes:EtOAc 7:3);
HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C36H31F12N4 747.2357; Found 747.2350.
Preparation and Characterization of Iron Complexes: General Procedure A. A flameꢀdried
10 mL Chemglass microwave vial, charged with a stir bar and ligand (1 equiv), was transferred
to a nitrogenꢀfilled glovebox where the solid mixture was treated with iron salt (1 equiv) and
acetonitrile (0.09 M). The red suspension was stirred for 16 h at 21 °C, after which point the red
solution was filtered using 0.2 ꢁM PTFE syringe filter and concentrated under reduced pressure
to obtain the iron complex. The iron complex was stored in glovebox freezer at –36 °C.
General Procedure B. A flameꢀdried 10 mL Chemglass microwave vial, charged with a stir bar
and ligand (1 equiv), was transferred to a nitrogenꢀfilled glovebox where the solid mixture was
treated with iron(II) chloride (1 equiv) and acetonitrile (0.09 M). The mixture was stirred for 16
h at 21 °C, after which point the orange solution was concentrated under reduced pressure to
obtain the iron complex. Then, iron complex (1 equiv) was treated with silver salt (2 equiv) and
acetonitrile (0.09 M). The mixture was stirred for an additional 12 h at 21 °C at which point it
was stored in glovebox freezer at –36 °C for 4 hours. After 4 h, the solution was filtered using
0.2 ꢁM PTFE syringe filter and concentrated under reduced pressure. The crude was dissolved in
acetonitrile (1.5 mL), filtered through a pad of celite, and then concentrated under reduced
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pressure. The concentrate was again dissolved in acetonitrile (1.5 mL), filtered through a pad of
celite, and then concentrated under reduced pressure.
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Complex (1a). Prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis((R)ꢀ(3,5ꢀdiꢀtertꢀbutylꢀphenyl)ꢀ2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (39.1 mg, 49.7 ꢁmol, 1 equiv) and iron(II) perchlorate
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hexahydrate (18.8 mg, 51.8 ꢁmol, 1 equiv) following general procedure A. The complex was
obtained as red solid (51.4 mg, quantative yield). Anal. Calcd for C48H68Cl2FeN4O8•2H2O: C,
58.13; H, 7.32; N, 5.65 %. Found: C, 58.38; H, 6.88; N, 5.45 %; HRMS (ESI–TOF) m/z: [M –
2H2O – 2ClO4]2+ Calcd for C48H68FeN4 378.2396; Found 378.2389. Complex (1a) was also
prepared from complex (1c) (102 mg, 0.12 mmol, 1 equiv) and silver perchlorate (51.1 mg, 0.24
mmol, 2 equiv) following general procedure B. The complex was obtained as a brown solid (115
mg, 98% yield).
Complex (1b). Prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis((R)ꢀ(3,5ꢀdiꢀtertꢀbutylꢀphenyl)ꢀ2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (0.3 mg, 71.7 ꢁmol, 1 equiv) and iron(II)
trifluoromethanesulfonate (25.4 mg, 71.7 ꢁmol, 1 equiv) following general procedure A. The
complex was obtained as a yellow solid (72 mg, 95% yield). Anal. Calcd for
C50H68F6FeN4O6S2•H2O: C, 55.96; H, 6.58; N, 5.22 %. Found: C, 55.69; H, 6.24; N, 5.06 %;
HRMS (ESI–TOF) m/z: [M – 2H2O – 2OTf]2+ Calcd for C48H68FeN4 378.2396; Found 378.2390.
Complex (1c). Prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis((R)ꢀ(3,5ꢀdiꢀtertꢀbutylꢀphenyl)ꢀ2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (97.8 mg, 0.139 mmol, 1 equiv) and iron(II) chloride
(17.6 mg, 0.139 mmol, 1 equiv) following general procedure A. The complex was obtained as an
orange solid (114 mg, quantative yield). Anal. Calcd for C48H68Cl2FeN4•1/2H2O: C, 68.89; H,
8.31; N, 6.70 %. Found: C, 68.70; H, 8.19, N, 6.65 %; HRMS (ESI–TOF) m/z: [M – Cl]+ Calcd
for C48H68ClFeN4 791.4482; Found 791.4478.
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Complex (1d). Prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis((R)ꢀ(3,5ꢀdiꢀtertꢀbutylꢀphenyl)ꢀ2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (97.8 mg, 0.139 mmol, 1 equiv), iron(II) chloride
(17.6 mg, 0.139 mmol, 1 equiv), and silver hexafluoroantimonate(V) (93.8 mg, 0.274 mmol, 2
equiv) following general procedure B. The complex was obtained as a red solid (180 mg,
quantative yield). Anal. Calcd for C48H68F12FeN4Sb2•3H2O: C, 44.95; H, 5.82; N, 4.37 %.
Found: C, 44.70; H, 5.41; N, 4.41 %; HRMS (ESI–TOF) m/z: [M – 2H2O – 2SbF6]2+ Calcd for
C48H68FeN4 378.2396; Found 378.2393.
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Complex
(1e).
Prepared
from
(1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis[Rꢀphenyl(2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (116 mg, 0.243 mmol, 1 equiv) and iron(II)
perchlorate hexahydrate (79.4 mg, 0.243 mmol, 1 equiv) following general procedure A. The
complex was obtained as a red solid (145 mg, 82% yield). Anal. Calcd for
C32H36Cl2FeN4O8•3H2O: C, 48.93; H, 5.39; N, 7.13 %. Found: C, 48.68; H, 4.93; N, 7.18 %;
HRMS (ESI–TOF) m/z: [M – 2H2O – 2ClO4]2+ Calcd for C32H36FeN4 266.1144; Found
266.1144.
Complex (1f). Prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis(2ꢀpyridinylmethyl)cyclohexaneꢀ
1,2ꢀdiamine (73.7 mg, 0.227 mmol, 1 equiv) and iron(II) perchlorate hexahydrate (82.6 mg,
0.227 mmol, 1 equiv) following general procedure A. The complex was obtained as a red solid
(136.4 mg, 91% yield). Anal. Calcd for C20H32Cl2FeN4O8•2.35H2O: C, 38.65; H, 5.30; N, 9.01
%. Found: C, 38.25; H, 4.89; N, 8.66 %. HRMS (ESI–TOF) m/z: [M – 2H2O – 2ClO4]2+ Calcd
for C22H32FeN4 190.0832; Found 190.0832.
Complex
(1g).
Prepared
from
(1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis(5ꢀtriisopropylsilyl)ꢀ2ꢀ
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (134 mg, 0.211 mmol, 1 equiv) and iron(II)
perchlorate hexahydrate (76.9 mg, 0.211 mmol, 1 equiv) following general procedure A. The
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complex was obtained as brownishꢀyellow solid (206 mg, quantative yield). Anal. Calcd for
C38H68Cl2FeN4O8Si2•(H2O)(MeCN): C, 50.52; H, 7.74; N, 7.36 %. Found: C, 50.69; H, 7.69; N,
7.48 %; HRMS (ESI–TOF) m/z: [M – 2H2O – 2ClO4]2+ Calcd for C38H68FeN4Si2 346.2160;
Found 346.2159. Complex (1g) was also prepared from (1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis(5ꢀ
triisopropylsilyl)ꢀ2ꢀpyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (41.7 mg, 0.0655 mmol, 1 equiv),
iron(II) chloride (8.30 mg, 0.065 mmol, 1 equiv) and silver perchlorate (27.1 mg, 0.13 mmol, 2
equiv) following general procedure B. The complex was obtained as red solid (58.3 mg, 98%
yield).
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Complex
(1h).
Prepared
from
(1R,2R)ꢀN,N′ꢀdimethylꢀN,N′ꢀbis(5ꢀtriisopropylsilyl)ꢀ2ꢀ
equiv), iron(II)
pyridinylmethyl)cyclohexaneꢀ1,2ꢀdiamine (34.2 mg, 53.7 ꢁmol,
1
trifluoromethanesulfonate (19.0 mg, 53.7 ꢁmol, 1 equiv), and acetonitrile (1 mL) following
general procedure A. The complex was obtained as a yellow solid (51 mg, 96% yield). Anal.
Calcd for C40H68F6FeN4O6S2Si2•H2O: C, 47.61; H, 6.99; N, 5.55 %. Found: C, 47.65; H, 6.91; N,
5.60 %; HRMS (ESI–TOF) m/z: [M – 2H2O – 2OTf]2+ Calcd for C38H68FeN4Si2 346.2160;
Found 346.2161.
Complex (1i). Prepared from (1R,2R)ꢀN,N′ꢀbis((5ꢀ(2,6ꢀbis(trifluoromethyl)phenyl)pyridineꢀ2ꢀ
yl)methyl)dimethyl cyclohexaneꢀ1,2ꢀdiamine (89.0 mg, 0.119 mmol, 1 equiv), iron(II)
perchlorate hexahydrate (43.2 mg, 0.119 mmol, 1 equiv) following general procedure A. The
complex was obtained as a red solid (113 mg, 88% yield). Anal. Calcd for
C36H32Cl2F12FeN4O8•H2O: C, 42.33; H, 3.36; N, 5.47; F, 22.32 %. Found: C, 42.66; H, 3.37; N,
5.71; F, 22.14 %; HRMS (ESI) m/z: [M – H2O – 2ClO4]2+ Calcd for C36H32F12FeN4 402.0892;
Found 402.0888.
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Complex (1j). Prepared from (2R,2R)ꢀ1,1′ꢀbis(pyridinꢀ2ꢀylmethyl)ꢀ2,2′ꢀbipyrrolidine (50.5 mg,
0.157 mmol, 1 equiv) and iron(II) perchlorate hexahydrate (56.4 mg, 0.157 mmol, 1 equiv)
following general procedure A. The complex was obtained as a red solid (89.7 mg, quantative
yield). Anal. Calcd for C20H26Cl2FeN4O8•2H2O: C, 39.17; H, 4.93; N, 9.14 %. Found: C, 39.42;
H, 4.70; N, 9.05 %; HRMS (ESI–TOF) m/z: [M – 2ClO4]2+ Calcd for C20H26FeN4 189.0754;
Found 189.0748.
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Complex (1k). Prepared from (2R,2R)ꢀ1,1′ꢀbis(5ꢀtriisopropylsilyl)pyridinꢀ2ꢀyl)methyl))ꢀ2,2′ꢀ
bipyrrolidine (100 mg, 0.157 mmol, 1 equiv) and iron(II) perchlorate hexahydrate (57.1 mg,
0.157 mmol, 1 equiv) following general procedure A. The complex was obtained as a red solid
(137 mg, quantative yield). Anal. Calcd for C38H66Cl2FeN4O8Si2•H2O: C, 50.27; H, 7.55; N, 6.17
%. Found: C, 49.99; H, 7.24; N, 6.25 %; HRMS (ESI–TOF) m/z: [M – 2ClO4]2+ Calcd for
C38H66FeN4Si2 345.2088; Found 345.2087.
Complex (1l). Prepared from (2R, 2′R)ꢀ1,1′ꢀbis((5ꢀ(3,5ꢀbis(trifluoromethyl)phenyl)pyridineꢀ2ꢀ
yl)methyl)ꢀ2,2′ꢀbipyrrolidine (50.0 mg, 0.067 mmol, 1 equiv) and iron(II) perchlorate
hexahydrate (24.3 mg, 0.067 mmol, 1 equiv) following general procedure A. The complex was
obtained as a red solid (62 mg, 92% yield). Anal. Calcd for C36H30Cl2FeF12N4O8•3H2O: C,
40.97; H, 3.44; N, 5.31; F, 21.60 %. Found: C, 41.23; H, 3.32; N, 5.35; F, 21.24 %; HRMS
(ESI–TOF) m/z: [M – 2MeCN – 2ClO4]2+ Calcd for C36H30F12FeN4 401.0809; Found 401.0808.
Complex (1m). Prepared from 1ꢀmethylꢀ2ꢀ((2R,2′R)ꢀ1′ꢀ(5ꢀtriisopropylsilyl)pyridineꢀ2ꢀ
yl)methyl)ꢀ2,2′ꢀbipyrrolidinꢀ1ꢀyl)methyl)ꢀ1Hꢀbenzo[d]imidazole (100 mg, 0.188 mmol, 1 equiv)
and iron(II) perchlorate hexahydrate (68.2 mg, 0.188 mmol, 1 equiv) following general
procedure A. The complex was obtained as a red solid (149 mg, quantative yield). Anal. Calcd
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for C32H49Cl2FeN5O8Si•H2O: C, 48.86; H, 6.28; N, 8.90 %. Found: C, 48.89; H, 6.49; N, 8.77 %.
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ꢀ 2+
HRMS (ESI) m/z: [M – H2O – 2ClO4 ] Calcd for C32H49FeN5Si 293.6553; Found 293.6549.
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Complex (1n). Prepared from (S)ꢀ1ꢀ(1ꢀethylꢀ1Hꢀbenzo[d]imidazolꢀ2ꢀyl)ꢀNꢀ((1ꢀ((1ꢀethylꢀ1Hꢀ
benzo[d]imidazolꢀ2ꢀyl)methyl)pyrrolidinꢀ2ꢀyl)methyl)ꢀNꢀmethylmethanamine (100 mg, 0.250
mmol, 1 equiv) and iron(II) perchlorate hexahydrate (92.6 mg, 0.255 mmol, 1 equiv) following
general procedure A. The complex was obtained as a red solid (164 mg, quantative yield). Anal.
Calcd for C24H30Cl2FeN6O8•1/2H2O: C, 43.26; H, 4.69; N, 12.61 %. Found: C, 43.08; H, 4.64;
N, 12.94 %; HRMS (ESI–TOF) m/z: [M – 2MeCN – 2ClO4]2+ Calcd for C24H30FeN6 229.0940;
Found 229.0935.
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Preparation and Characterization of Iminoiodinanes.
[Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane (4a). The compound was prepared according
to a modified literature procedure.32 A flameꢀdried 250 mL round bottom flask was charged with
a stir bar, 4ꢀnitrobenzenesulfonamide (1.25 g, 6.18 mmol, 1 equiv), potassium hydroxide (0.706
g, 12.58 mmol, 2 equiv), and methanol (150 mL). The yellow suspension was stirred at 21 °C
until all of the solid was dissolved. Then, diacetoxyiodobenzene (2.5 g, 7.78 mmol, 1.25 equiv)
was added to the clear yellow solution and the mixture was stirred at 21 °C for 4 h. The resulting
yellow precipitate was filtered, washed with water (3 x 100 mL) and methanol (3 x 100 mL), and
dried under reduced pressure over P2O5 overnight to obtain product as pale yellow solid (1.55g,
1
62% yield). The compound could be stored at 2–8 °C up to 3–5 weeks. H NMR (400 MHz, d6ꢀ
DMSO) δ 8.03 (d, J = 7.7, 1H), 7.71 (t, J = 7.7 Hz, 4H), 7.40 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.8
Hz, 2H).
[Nꢀ(4ꢀtertꢀbutylbenzenesulfonyl)imino]phenyliodinane (4c). The compound was prepared
according to a modified literature procedure.33 A flameꢀdried 250 mL round bottom flask was
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charged with a stir bar, 4ꢀtertꢀbutyl benzene sulfonamide (166 mg, 0.78 mmol, 1 equiv),
potassium hydroxide (87.5 mg, 1.56 mmol, 2 equiv), and methanol (20 mL). The solution was
cooled to 0 °C (ice/water bath), and diacetoxyiodobenzene (250 mg, 0.78 mmol, 1 equiv) was
added to the clear yellow solution and the mixture was stirred at 0 °C for 3 h. The resulting
yellow solution was poured into chilled 30 mL deionized water causing precipitate to form. The
suspension was left to settle for an hour in the freezer (2–8 ºC). The resulting yellow precipitate
was then filtered, washed with hexanes (30 mL) and dried under reduced pressure over P2O5
overnight to obtain product as yellow solid (192 mg, 59% yield). The compound could be stored
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stored at 2–8 °C up to 3–5 weeks. H NMR (500 MHz, d6ꢀDMSO) δ 7.64 (d, J = 7.4 Hz, 2H),
7.46 (d, J = 7.8 Hz, 2H), 7.41 (t, J = 7.4 Hz, 1H), 7.27–7.23 (m, 4H), 1.24 (s, 9H); 13C NMR (126
MHz, CDCl3) δ 152.9, 142.1, 133.1, 130.5, 130.1, 125.9, 124.9, 116.7, 34.4, 30.9; IR (neat) 2964
(w), 2867 (w), 1364 (w) cmꢀ1;HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C16H18INO2S
415.0103; Found 415.0103.
Preparation and Characterization of Olefins.
4ꢀvinylꢀ1, 1’ꢀbiphenyl (2a). The compound was prepared according to a modified literature
procedure.34 A flameꢀdried 250 mL round bottom flask was charged with a stir bar, phenyl
boronic acid (2.45 g, 20.1 mmol, 1.2 equiv), tri(oꢀtolyl)phosphine (0.51 g, 1.69 mmol, 0.1 equiv),
and barium hydroxide octahydrate (6.34 g, 20.1 mmol, 1.2 mmol). The flask was equipped with
a reflux condenser, sealed with a rubber septum and transferred to glovebox where palladium
acetate (0.92 g, 4.1 mmol, 0.05 equiv) was added to the flask. The sealed flask was then removed
from the glovebox. 4ꢀvinylbromobenzene (2.20 mL, 16.83 mmol, 1 equiv), dimethoxyethane (80
mL) and degassed DI water (30 mL) were added sequentially to the reaction via syringe. The
suspension was then stirred at 80 °C for 4 hours under nitrogen atmosphere. The black
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suspension was vacuum filtered and the filtrate was concentrated under reduced pressure to
remove dimethoxymethane. The aqueous suspension was transferred to a separatory funnel and
extracted with dichloromethane (3 x 50 mL). The combined organic layers were dried over
Na2SO4, filtered, and concentrated under reduced pressure to obtain a pale white solid. The pale
white solid was purified by silica gel column chromatography using hexanes to obtain the
desired product as a white solid (2.65 g, 88% yield). The compound was stored at 2–8 °C. The
characterization data for the compound were in agreement with previously published
information.35 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 6.9, 2H), 7.57 (d, J = 8.3 Hz, 2H); 7.49
(d, J = 8.3 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 6.76 (dd, J = 17.6, 10.9 Hz,
1H), 5.80 (d, J = 17.6 Hz, 1H), 5.28 (d, J = 10.9 Hz, 1H).
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6ꢀmethylꢀ2ꢀ(4ꢀvinylphenyl)ꢀ1,3,6,2ꢀdioxazaborocaneꢀ4,8ꢀdione (2j). The compound was prepared
according to the modified literature procedure.36 A 500 mL round bottom flask was charged with
a stir bar, flameꢀdried under vacuum and allowed to cool to 21 °C under nitrogen atmosphere. 4ꢀ
vinylphenylboronic acid (0.500 g, 3.39 mmol, 1.0 equiv) and Nꢀmethyliminodiacetic acid (0.497
g, 3.39 mmol, 1.0 equiv) were added to the flask and the flask was equipped with a reflux
condenser and sealed with a rubber septum. It was thrice evacuated under vacuum and backfilled
with nitrogen. The mixture of solids was treated with benzene (55 mL) and DMSO (6 mL) via
syringe and the resulting mixture was refluxed 80 °C under nitrogen atmosphere for 16 h. The
yellow solution was concentrated under reduced pressure to remove benzene and the remaining
solution was diluted with deionized water (50 mL). A precipitate formed immediately. The
aqueous suspension was transferred to a separatory funnel and extracted with ethyl acetate (3 x
50 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under
reduced pressure to obtain a crude liquid which was purified by silica gel column
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chromatography using hexanes:EtOAc (2:8) to obtain the desired product as a white solid (0.64
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g, 74% yield). H NMR (500 MHz, CDCl3) δ 7.50–7.21 (m, 4H), 6.75 (dd, J = 17.7, 10.9 Hz,
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1H), 5.82 (d, J = 17.6 Hz, 1H), 5.24 (d, J = 10.9 Hz, 1H), 4.25 (d, J = 16.9 Hz, 2H), 4.06 (d, J =
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16.8 Hz, 2H), 2.56 (s, 3H) ; C NMR (126 MHz, CDCl3) δ 169.2, 139.0, 137.4, 133.5, 126.3,
114.6, 62.5, 48.1 ; IR (neat) ν 3106 (w), 2926 (w), 2858 (w), 1742 (s), 1608 (w) cmꢀ1; TLC Rf =
0.5 (EtOAc); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C13H14BNO4 260.1089; Found
260.1090.
2ꢀ(3,5ꢀdiꢀtertꢀbutylꢀ2ꢀ((3ꢀvinylbenzyl)oxy)phenyl)acetonitrile (2k). The compound was prepared
according to the modified literature procedure.37 A flameꢀdried 50 mL round bottom flask was
charged with 2ꢀ(3,5ꢀdiꢀtertꢀbutylꢀ2ꢀhydroxyphenyl)acetonitrile (764 mg, 3.12 mmol, 1.0 equiv),
dry DMF (11 mL) and the solution was chilled in an ice/water bath at 0 °C. Sodium hydride
(60% w/w, 140 mg, 3.5 mmol, 1.1 equiv) was added to the solution at 0 °C. Once effervescence
stopped, 1ꢀ(bromomethyl)ꢀ3ꢀvinylbenzene (612 mg, 3.12 mmol, 1 equiv) was added dropwise
via syringe at 0 °C under nitrogen atmosphere and the reaction was stirred for 5h. The reaction
was quenched by the addition of deionized water (10 mL) and the layers were separated. The
aqueous layer was then extracted with diethyl ether (3 x 15 mL). The combined organic layers
were washed with deionized water (3 x 15 mL), dried over Na2SO4, filtered, and concentrated
under reduced pressure to obtain an orange solid. The crude orange solid was purified by silica
gel column chromatography using hexanes:EtOAc (9:1), to obtain the desired product as a white
solid (0.367 g, 33% yield). 1H NMR (400 MHz, CDCl3) δ 7.52 (s, 1H), 7.43 – 7.38 (m, 4H), 7.34
– 7.33 (m, 1H), 6.77 (dd, J = 18.1, 11.1 Hz, 1H), 5.81 (d, J = 17.9 Hz, 1H), 5.30 (d, J = 11.1 Hz,
13
1H), 4.90 (s, 2H), 3.73 (s, 2H), 1.44 (s, 9H), 1.34 (s, 9H); C NMR (126 MHz, CDCl3) δ 153.7,
147.3, 143.0, 138.2, 137.5, 136.8, 129.1, 126.1, 125.9, 125.3, 125.1, 124.5, 123.9, 114.4, 75.5,
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35.8, 34.9, 31.6, 31.5, 19.4; IR (neat) ν 3001 (w), 2958 (m), 2901 (w), 2866 (w), 2251 (w), 1602
(w) cmꢀ1; TLC Rf = 0.2 (hexanes: EtOAc, 9:1); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for
C25H31NO 361.2406; Found 361.2408.
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Preparation and Characterization of Aziridines.
General Procedure for Aziridination. Reactions were performed on 0.25 mmol scale, unless
otherwise specified. A flameꢀdried 10 mL Chemglass microwave vial was charged with a stir
bar, 4ꢀvinylbiphenyl (45.1 mg, 0.25 mmol, 1 equiv), and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]
phenyliodinane (151 mg, 0.375 mmol, 1.5 equiv). The vial was transferred to a nitrogenꢀfilled
glovebox where iron complex (12.13 mg, 0.0125 mmol, 5 mol %) and acetonitrile (1.5 mL) were
added to the vial. The resulting orange suspension was stirred at 21 °C for 1.5 h, after which
point the reaction was concentrated under reduced pressure. The desired product was isolated by
silica gel column chromatography (conditions given below). Deviations from this procedure are
specified below.
2ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridine (3a). Prepared from 4ꢀvinylbiphenyl
and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the general procedure for
aziridination. The product was obtained as a white solid (68.2 mg, 71% yield) after silica gel
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column chromatography using hexanes:EtOAc (9:1). H NMR (400 MHz, CDCl3) δ 8.4 (d, J =
8.5 Hz, 2H), 8.21 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 8.4 Hz, 4H), 7.43 (t, J = 7.6 Hz, 2H), 7.37 –
7.34 (m, 1H), 7.29 (d, J = 7.9 Hz, 2H), 3.95 (dd, J = 4.7, 7.2 Hz, 1H), 3.15 (d, J = 7.2 Hz, 1H),
2.55 (d, J = 4.6 Hz, 1H) ; 13C NMR (126 MHz, CDCl3) δ 150.9, 144.1, 142.0, 140.4, 133.3,
129.4, 129.1, 127.8, 127.7, 127.2, 127.1, 125.6, 41.9, 36.8 ; IR (neat) ν 3103 (w), 3032 (w), 2869
(w), 1527 (s), 1347 (m), 1333 (m), 1161 (s) cmꢀ1; TLC Rf = 0.17 (hexanes:EtOAc, 9:1); HRMS
(ESI–TOF) m/z: [M + H]+ Calcd for C20H16N2O4S 380.0831; Found 380.0830.
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2ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀ1ꢀtosylaziridine (3b). Prepared from 4ꢀvinylbiphenyl and 4ꢀmethylꢀNꢀ
(phenylꢀλ3ꢀiodaneylidene)pyridineꢀ2ꢀsulfonamide following the general procedure for
aziridination. The product was obtained as a white solid (56.1 mg, 64% yield) after silica gel
column chromatography using hexanes:EtOAc (9:1). The characterization data for the
compound were in agreement with previously published information.38 1H NMR (500 MHz,
CDCl3) δ 7.89 (d, J = 8.3 Hz, 2H), 7.57 – 7.49 (m, 4H), 7.43 (t, J = 7.6 Hz, 2H), 7.35 (dd, J =
7.8, 2.6 Hz, 3H), 7.29 (d, J = 8.2 Hz, 2H), 3.82 (dd, J = 7.2, 4.5 Hz, 1H), 3.02 (d, J = 7.2 Hz,
1H), 2.44 – 2.43 (m, 4H).
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2ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀ1ꢀ((4ꢀ(tertꢀbutyl)phenyl)sulfonyl)aziridine (3c). Prepared from 4ꢀ
vinylbiphenyl and 4ꢀ(tertꢀbutyl)ꢀNꢀ(phenylꢀλ3ꢀiodaneylidene)pyridineꢀ2ꢀsulfonamide following
the general procedure for aziridination. The product was obtained as a white solid (51 mg, 52%
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yield) after silica gel column chromatography using hexanes:EtOAc (9:1). H NMR (500 MHz,
CDCl3) δ 7.92 (d, J = 8.2 Hz, 2H), 7.57 – 7.52 (m, 6H), 7.43 (t, J = 7.6 Hz, 2H), 7.36 – 7.31 (m,
1H), 7.31 (d, J = 7.9 Hz, 2H), 3.85 (dd, J = 4.5, 7.2 Hz, 1H), 3.02 (d, J = 7.2 Hz, 1H), 2.44 (d, J
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= 4.5 Hz, 1H), 1.35 (s, 9H) ; C NMR (126 MHz, CDCl3) δ 157.8, 141.5, 140.7, 135.1, 134.3,
129.0, 128.0, 127.7, 127.5, 127.3, 126.4, 41.0, 36.3, 35.5, 31.3 ; IR (neat) ν 2962 (s), 2868 (w),
1359 (s), 1158 (m) cmꢀ1; TLC Rf = 0.14 (hexanes:EtOAc, 9:1); HRMS (ESI–TOF) m/z: [M +
H]+ Calcd for C24H25NO2S 391.1606; Found 391.1605.
1ꢀ((4ꢀnitrophenyl)sulfonyl)ꢀ2ꢀphenylaziridine (3d). Prepared from styrene and [Nꢀ(4ꢀ
nitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
aziridination. The product was obtained as a white solid (56 mg, 73% yield) after silica gel
column chromatography using hexanes:EtOAc (9:1). The characterization data for the
compound were in agreement with previously published information.39 1H NMR (400 MHz,
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CDCl3) δ 8.37 (d, J = 8.8 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H), 7.31 (m, 3H), 7.22 (m, 2H), 3.90
(dd, J = 7.2, 4.4 Hz, 1H), 3.11 (d, J = 7.6 Hz, 1H), 2.50 (d, J = 4.4 Hz, 1H).
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1ꢀ((4ꢀnitrophenyl)sulfonyl)ꢀ2ꢀphenylaziridine (3e). Prepared from 4ꢀacetoxystyrene and [Nꢀ(4ꢀ
nitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
aziridination. The product was obtained as a white solid (62.5 mg, 69% yield) after silica gel
column chromatography using hexanes:EtOAc (9:1). The characterization data for the
compound were in agreement with previously published information.14d 1H NMR (400 MHz,
CDCl3) δ 8.39 (d, J = 8.8 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 8.6 Hz, 2H), 7.04 (d, J =
8.5 Hz, 2H), 3.89 (dd, J = 7.2, 4.5 Hz, 1H), 3.11 (d, J = 7.2 Hz, 1H), 2.29 (s, 2H).
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2ꢀ(4ꢀtertꢀbutyl)phenyl)ꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridine
(3f).
Prepared
from
4ꢀ
tertbutylstyrene and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3h following the
general procedure for aziridination. The product was obtained as a white solid (56.1 mg, 62%
yield) after silica gel column chromatography using hexanes:EtOAc (9:1). The characterization
data for the compound were in agreement with previously published information.39 1H NMR
(400 MHz, CDCl3) δ 8.38 (d, J = 8.9 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H),
7.14 (d, J = 8.3 Hz, 2H), 3.89 (dd, J = 7.3, 4.7 Hz, 1H), 3.10 (d, J = 7.2 Hz, 1H), 2.51 (d, J = 4.7
Hz, 1H), 1.29 (s, 1H).
2ꢀ(4ꢀbromophenyl)ꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridine (3g). Prepared from 4ꢀbromostyrene and
[Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the general procedure for
aziridination. The product was obtained as a an offꢀwhite (56.5 mg, 59% yield) after silica gel
column chromatography using hexanes:EtOAc (9:1). The characterization data for the
compound were in agreement with previously published information.39 1H NMR (400 MHz,
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CDCl3) δ 8.39 (d, J = 8.8 Hz, 2H), 8.18 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H), 7.10 (d, J =
8.4 Hz, 2H), 3.86 (dd, J = 7.1, 4.4 Hz, 1H), 3.11 (d, J = 7.3 Hz, 1H), 2.46 (d, J = 4.6 Hz, 1H).
4ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridineꢀ2ꢀyl)benzonitrile (3h). Prepared from 4ꢀcyanostyrene and
[Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
aziridination. The product was obtained as a pale yellow solid (52.4 mg, 61% yield) after silica
gel column chromatography using hexanes:EtOAc (9:1). The characterization data for the
compound were in agreement with previously published information.14d 1H NMR (400 MHz,
CDCl3) δ 8.41 (d, J = 8.8 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H), 7.63 (d, J = 8.3 Hz, 2H), 7.36 (d, J =
8.2 Hz, 2H), 3.94 (dd, J = 7.2, 4.4 Hz, 1H), 3.14 (d, J = 7.3 Hz, 1H), 2.46 (d, J = 4.4 Hz, 1H).
2ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridineꢀ2ꢀyl)benzonitrile (3i). Prepared from 2ꢀcyanostyrene and
[Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
aziridination. The product was obtained as a pale yellow solid (55.2 mg, 67% yield) after silica
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gel column chromatography using hexanes:EtOAc (9:1). H NMR (500 MHz, CDCl3) δ 8.43 –
8.40 (m, 2H), 8.25 – 8.22 (m, 2H), 7.65 (d, J = 8.0 Hz, 1H), 7.56 (td, J = 7.7, 1.1 Hz, 1H), 7.42
(td, J = 7.7, 1.1 Hz, 1H), 7.29 (d, J = 8.2 Hz, 1H), 4.19 (dd J = 7.0, 4.6 Hz, 1H), 3.22 (d, J = 7.1
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Hz, 1H), 2.52 (d, J = 4.6 Hz, 1H) ; C NMR (126 MHz, CDCl3) δ 151.1, 143.4, 138.1, 133.5,
133,2, 129.7, 129.3, 126.7, 124.7, 116.9, 112.3, 39.5, 36.8 ; IR (neat) ν 3107 (w), 2924 (w), 2227
(w), 1529 (s), 1340 (m), 1310 (m), 1165 (s) cmꢀ1; TLC Rf = 0.14 (hexanes:EtOAc, 8:2); HRMS
(ESI–TOF) m/z: [M + H]+ Calcd for C15H11N3O4S 329.0470; Found 329.0470.
6ꢀmethylꢀ2ꢀ(4ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridinꢀ2ꢀyl)phenyl)ꢀ1,3,6,2ꢀdioxazaborocaneꢀ4,8ꢀ
dione (3j). Prepared from 6ꢀmethylꢀ2ꢀ(4ꢀvinylphenyl)ꢀ1,3,6,2ꢀdioxazaborocaneꢀ4,8ꢀdione (2j)
and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the general procedure for
aziridination. The product was obtained as a white solid (63 mg, 55% yield) after silica gel
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column chromatography using hexane:EtOAc (3:7). H NMR (400 MHz, CD3CN) δ 8.38 (d, J =
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8.7 Hz, 1H), 8.18 (d, J = 8.8 Hz, 1H), 7.46 (d, J = 7.7 Hz, 1H), 7.27 (d, J = 7.7 Hz, 1H), 4.05 (d, J
= 17.1 Hz, 1H), 3.97 – 3.80 (m, 2H), 3.05 (d, J = 7.3 Hz, 1H), 2.64 (d, J = 4.6 Hz, 1H), 2.46 (s,
2H); 13C NMR (126 MHz, CD3CN) δ 169.2, 151.7, 143.9, 136.3, 133.5, 130.0, 126.9, 125.3,
62.5, 48.2, 41.9, 37.0; IR (neat) ν 2957 (w), 2925 (w), 2856 (w), 1731 (m), 1529 (m), 1334 (m),
1161 (s) cmꢀ1; TLC Rf = 0.24 (hexanes:EtOAc, 2:8); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for
C19H18BN3O8S 460.0980; Found 460.0977.
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2ꢀ(3,5ꢀdiꢀtertꢀbutylꢀ2ꢀ((3ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridinꢀ2ꢀyl)benzyl)oxy)phenyl)
acetonitrile (3k). Prepared from 2ꢀ(3,5ꢀdiꢀtertꢀbutylꢀ2ꢀ((3ꢀvinylbenzyl)oxy)phenyl)acetonitrile
(2k) and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3 h following the general
procedure for aziridination. The product was obtained as a white solid (80.2 mg, 58% yield) after
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silica gel column chromatography using hexane:EtOAc (9:1). H NMR (500 MHz, CDCl3) δ
8.39 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.4 Hz, 2H), 7.48 – 7.42 (m, 1H), 7.42 – 7.35 (m, 3H), 7.31
(d, J = 2.4 Hz, 1H), 7.23 (dt, J = 7.4, 1.6 Hz, 1H), 4.88 (s, 2H), 3.97 (dd, J = 7.2, 4.6 Hz, 1H),
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3.68 (s, 2H), 3.14 (d, J = 7.2 Hz, 1H), 2.55 (d, J = 4.5 Hz, 1H), 1.41 (s, 9H), 1.33 (s, 9H) ; C
NMR (126 MHz, CDCl3) δ 153.5, 150.9, 147.4, 144.0, 142.9, 138.0, 135.0, 129.4, 129.3, 126.9,
126.2, 125.4, 125.2, 124.6, 124.5, 123.7, 118.8, 75.0, 41.8, 37.0, 35.7, 34.8, 31.6, 31.5, 19.3 ; IR
(neat) ν 3104 (w), 3056 (w), 2962 (w), 2869 (w), 1532 (m), 1348 (w), 1337 (w), 1164 (w) cmꢀ1;
TLC Rf = 0.12 (hexanes:EtOAc, 7:1); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C31H35N3O5S
561.2297; Found 561.2297.
(8R,9S,13S,14S)ꢀ13ꢀmethylꢀ3ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridinꢀ2ꢀyl)ꢀ
6,7,8,9,11,12,13,14,15,16ꢀdecahydroꢀ17Hꢀcyclopenta[a]phenanthrenꢀ17ꢀone (3l). Prepared from
(8R,9S,13S,14S)ꢀ13ꢀmethylꢀ3ꢀvinylꢀ6,7,8,9,11,12,13,14,15,16ꢀdecahydroꢀ17Hꢀ
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cyclopenta[a]phenanthrenꢀ17ꢀone
and
[Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane
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following the general procedure for aziridination. The product was obtained as an off white solid
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(53 mg, 44% yield) after silica gel column chromatography using hexane:EtOAc (8:2). H NMR
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(400 MHz, CDCl3) δ 8.38 (d, J = 8.8 Hz, 2H), 8.18 (d, J = 8.8 Hz, 2H), 7.24 (d, J = 8.4 Hz, 1H),
6.99 (dd, J = 8.1, 2.1 Hz, 1H), 6.95 (d, J = 1.9 Hz, 1H), 3.85 (dd, J = 7.2, 4.6 Hz, 1H), 3.08 (d, J
= 7.2 Hz, 1H), 2.87 (dd, J = 8.9, 4.3 Hz, 2H), 2.53 – 2.47 (m, 2H), 2.41 – 2.22 (m, 3H), 2.19 –
1.92 (m, 6H), 1.60 – 1.44 (m, 6H), 0.89 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 220.6, 150.6,
144.0, 140.6, 137.1, 131.5, 129.2, 127.0, 127.0, 125.8, 124.3, 123.8, 123.8, 50.4, 47.8, 44.3, 41.8,
41.7, 38.0, 36.4, 35.8, 31.5, 29.3, 26.3, 25.6, 21.5, 13.8; IR (neat) ν 3106 (w), 2925 (w), 2857
(w), 1741 (m), 1527 (m), 1347 (m), 1325 (m), 1157 (s) cmꢀ1; TLC Rf = 0.32 (hexanes:EtOAc,
8:2); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C26H28N2O5S 481.1792; Found 481.1792.
2ꢀ(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridinꢀ2ꢀyl)pyridine (3m). Prepared from 2ꢀvinylpyridine and [Nꢀ
(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
aziridination. The product was obtained as an orange solid (35 mg, 46% yield) after silica gel
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column chromatography using hexane:EtOAc (5:5). H NMR (400 MHz, CDCl3) δ 8.59 – 8.49
(m, 1H), 8.43 – 8.32 (m, 2H), 8.24 – 8.16 (m, 2H), 7.67 (td, J = 7.7, 1.8 Hz, 1H), 7.34 – 7.19 (m,
13
2H), 4.03 (dd, J = 7.3, 4.5 Hz, 1H), 3.11 (d, J = 7.3 Hz, 1H), 2.83 (d, J = 4.5 Hz, 1H); C NMR
(126 MHz, CDCl3) δ 153.2, 150.7, 149.9, 143.6, 136.9, 129.4, 124.3, 123.7, 122.0, 42.0, 35.4; IR
(neat) ν 3105 (w), 2924 (w), 1530 (m), 1350 (m), 1310 (w), 1166 (s) cmꢀ1; TLC Rf = 0.25
(hexanes:EtOAc, 7:3); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C13H11N3O4S 306.0543;
Found 306.0544.
2ꢀHexylꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridine (3n). Prepared from 1ꢀoctene and [Nꢀ(4ꢀ
nitrobenzenesulfonyl)imino]phenyliodinane after 3h following the general procedure for
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aziridination. The product was obtained as a white solid (21 mg, 27% yield) after silica gel
column chromatography using hexane:EtOAc (9:1). The characterization data for the compound
were in agreement with previously published information.40 1H NMR (400 MHz, CDCl3) δ 8.39
(d, J = 8.7 Hz, 2H), 8.16 (d, J = 8.7 Hz, 2H), 2.88 (tt, J = 7.2, 4.9 Hz, 1H), 2.74 (d, J = 7.1 Hz,
1H), 2.16 (d, J = 4.7 Hz, 1H), 1.63 – 1.52 (m, 2H), 1.45 – 1.31 (m, 2H), 1.30 – 1.16 (m, 8H),
0.85 (t, J = 6.9 Hz, 3H).
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(1ꢀ((4ꢀnitrophenyl)sulfonyl)aziridinꢀ2ꢀyl)(phenyl)methanone (3o). Prepared from 1ꢀphenylpropꢀ
2ꢀenꢀ1ꢀone and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the general
procedure for aziridination. The product was obtained as a white solid (34 mg, 41% yield) after
1
silica gel column chromatography using hexane:EtOAc (8:2). H NMR (400 MHz, CDCl3) δ
8.45 – 8.32 (m, 1H), 8.25 – 8.16 (m, 1H), 8.11 – 8.02 (m, 1H), 7.66 (t, J = 7.5 Hz, 1H), 7.53 (t, J
= 7.8 Hz, 1H), 4.32 (dd, J = 7.0, 4.3 Hz, 1H), 3.00 (d, J = 7.0 Hz, 1H), 2.84 (d, J = 4.3 Hz, 1H);
13C NMR (126 MHz, CDCl3) δ 190.5, 150.9, 143.2, 135.3, 134.5, 129.3, 129.0, 128.8, 124.4,
38.0, 33.4; IR (neat) ν 3098 (w), 3029 (w), 2919 (w), 1698 (m), 1523 (m), 1349 (m), 1308 (m),
1163 (s) cmꢀ1; TLC Rf = 0.13 (hexanes:EtOAc, 9:1); HRMS (ESI) m/z: [M + H]+ Calcd for
C15H13N2O5S 333.0545; Found 333.0538.
(2S,3R)ꢀ2ꢀmethylꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)ꢀ3ꢀphenylaziridine (3p). Prepared from (Z)ꢀpropꢀ1ꢀ
enꢀ1ꢀylbenzene (>5:95 E:Z) and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the
general procedure for aziridination. The crude product was obtained as a 15:85 (E/Z) mixture of
diastereomers. After column chromatography, the product was isolated as a white solid (32 mg,
40% yield, 9:91 (E:Z)) using hexanes:EtOAc (9:1). The characterization data for the compound
were in agreement with previously published information.41 1H NMR (400 MHz, CDCl3) δ 8.39
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(d, J = 8.8 Hz, 2H), 8.21 (d, J = 8.8 Hz, 2H), 7.34 – 7.27 (m, 3H), 7.19 (dd, J = 7.4, 2.3 Hz, 2H),
4.07 (d, J = 7.3 Hz, 1H), 3.34 (dq, J = 7.3, 5.8 Hz, 1H), 1.07 (d, J = 5.8 Hz, 3H).
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(2S,3R)ꢀ2ꢀmethylꢀ1ꢀ((4ꢀnitrophenyl)sulfonyl)ꢀ3ꢀphenylaziridine (3q). Prepared from (Z)ꢀpropꢀ1ꢀ
enꢀ1ꢀylbenzene (>95:5 E:Z) and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane following the
general procedure for aziridination. The product was obtained as a white solid (18 mg, 22%
yield) in 95:5 (E/Z) after silica gel column chromatography using hexane:EtOAc (9:1). The
characterization data for the compound were in agreement with previously published
information.41 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.8 Hz, 2H), 8.11 (d, J = 8.8 Hz, 2H),
7.30 – 7.26 (m, 3H), 7.13 (dd, J = 6.7, 3.0 Hz, 2H), 3.87 (d, J = 4.4 Hz, 1H), 3.06 (qd, J = 5.9,
4.2 Hz, 1H), 1.88 (d, J = 5.9 Hz, 3H).
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N4, N4, N4’, N4’ꢀtetramethylꢀ[1,1’ꢀbiphenyl]ꢀ4,4’ꢀdiamine (7). Prepared from N,N’ꢀ
dimethylaniline and [Nꢀ(4ꢀnitrobenzenesulfonyl)imino]phenyliodinane after 3h following the
general procedure for aziridination. The product was obtained as a white solid (13.7 mg, 46%
yield) after silica gel column chromatography using hexane:EtOAc (98:2). The characterization
data for the compound were in agreement with previously published information.42 1H NMR
(400 MHz, CDCl3) δ 7.45 (d, J = 8.8 Hz, 4H), 6.80 (d, J = 8.3 Hz, 4H), 2.97 (s, 12H).
2,2,2ꢀtrichloroethyl 2ꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)aziridineꢀ1ꢀsulfonate (11). Prepared from 4ꢀ
vinylbiphenyl and [Nꢀ(2,2,2ꢀtrichloroethyoxysulfonyl)imino]phenyliodinane following the
general procedure for aziridination. The product was obtained as a white solid (28.5 mg, 28%
1
yield) after silica gel column chromatography using hexanes:EtOAc (9:1). H NMR (400 MHz,
CDCl3) δ 7.62 – 7.59 (m, 4H), 7.45 (t, J = 7.6 Hz), 7.40 – 7.37 (m, 3H), 4.88 (ABq, ꢀδAB =0.06,
JAB = 10.6 Hz, 2H), 3.92 (dd, J = 7.0 Hz, 4.7 Hz, 2H), 3.13 (d, J = 7.1 Hz, 1H), 2.67 (d, J = 4.7
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Hz, 1H); C NMR (126 MHz, CDCl3) δ 141.9, 140.2, 132.7, 128.9, 127.7, 127.5, 127.1, 127.0,
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92.8, 79.7, 42.6, 37.5; IR (neat) ν 3031 (w), 2955 (w), 1368 (m), 1180 (m) cmꢀ1; TLC Rf = 0.3
(hexanes:EtOAc, 8:2); HRMS (ESI–TOF) m/z: [M + H]+ Calcd for C16H15Cl3NO3S 405.9838;
Found 405.9835.
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ASSOCIATED CONTENT
The Supporting Information is available free of charge on the ACS Publications website.
Copies of NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Author
*j.roizen@duke.edu
ORCID
J. L. Roizen: 0000ꢀ0002ꢀ6053ꢀ5512
Author Contributions
†M.F.S. and S.K.A. contributed equally.
The manuscript was written through contributions of all authors. All authors have given approval
to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
This project was funded by the American Chemical Society Petroleum Research Fund Doctoral
New Investigator Program (PRF# 54824ꢀDNI1) and by Duke University. M.F.S. was supported
in part by the Kathleen Zielik fellowship. Characterization data were obtained on instrumentation
secured by funding from the NSF (CHEꢀ0923097, ESIꢀMS, George Dubay, the Duke Dept. of
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