Intrinsically Safe and Shelf-Stable Diazo-Transfer ... - ACS Publications

Aug 18, 2018 - presence of excess organic base such as triethylamine.10. However, some .... gave the best performance of 93% NMR yield of diazo produc...
0 downloads 0 Views 435KB Size
Download PDF
Subscriber access provided by Kaohsiung Medical University

Article

An Intrinsically Safe and Shelf-stable Diazo-Transfer Reagent for Fast Synthesis of Diazo Compounds Shibo Xie, Ziqiang Yan, Yuanheng Li, Qun Song, and Mingming Ma J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01587 • Publication Date (Web): 18 Aug 2018 Downloaded from http://pubs.acs.org on August 19, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Organic Chemistry

An Intrinsically Safe and Shelf-stable Diazo-Transfer Reagent for Fast Synthesis of Diazo Compounds Shibo Xie,# Ziqiang Yan,# Yuanheng Li, Qun Song, Mingming Ma* CAS Key Laboratory of Soft Matter Chemistry, iChEM (Innovation Center of Chemistry for Energy Materials), Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China. # Equal contribution. Supporting Information Placeholder N3 N O

N N

R1 O

R 2 Inorganic base 40 mol% DMSO, 25 °C, 2∼ 6 min

ADT, Intrinsically safe solid stable for > 1 year at RT

R1

R2 N2

R 1,R 2= carbonyl, aryl, phosphoryl 14 examples, isolation yield 70 ∼98%

ABSTRACT: We report a crystalline compound 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT) as an intrinsically safe, highly efficient and shelf-stable diazo-transfer reagent. Since the decomposition of ADT is an endothermal process (∆H = 30.3 kJ mol-1), ADT is intrinsically nonexplosive, as proved by thermal, friction and impact tests. The diazo-transfer reaction based on ADT gives diazo compounds in excellent yields within several minutes at room temperature. ADT is very stable upon >1 year storage under air at room temperature.

Introduction Diazo compounds are versatile building blocks in organic synthesis, since they can serve as precursors for carbenes and carbenoids, which give rise to a wide variety of chemical transformations with a remarkable degree of chemo-, regio-, and stereo-selectivity.1-4 Diazo groups are also found in natural products and amino acids that show unique antimicrobial and antitumor activities.5-7 Particularly, stabilized diazo compounds in which the electrons on α- carbon are delocalized onto adjacent functional groups (e.g. carbonyl and aromatic groups)8 are compatible with living systems, and have great potentials for widespread applications in chemical biology.9 One efficient method of synthesizing stabilized diazo compounds is diazo-transfer reaction of active methylene compound.8 Sulfonyl azides are commonly used as diazo transfer reagents, and the reaction proceeds typically in the presence of excess organic base such as triethylamine.10 However, some sulfonyl azides such as p-tosyl azide and trifluoromethanesulfonyl azide are impact sensitive and highly explosive. Aiming at safer reagents, chemists have developed many new sulfonyl azides, including mesyl azide,11 p-dodecylbenzenesulfonyl azide,12 polystyrene-supported benzenesulfonyl azide,13 and heteroarylsulfonyl azide (e.g. imidazole-1-sulfonyl azide hydrochloride14 and benzotriazole-1-sulfonyl azide15). Although the stability of these new sulfonyl azides are generally better than that of p-tosyl azide, serious concerns about the safety of their preparation have been raised,16 such as the generation of highly explosive and toxic hydrazoic acid and sulfuryl diazide. To overcome these issues of sulfonyl azides, 2-azide-1,3dimethylimidazolinium salts (ADM) has been developed as a new class of diazo-transfer reagent.17-18 These ADM reagents

Figure 1. Synthesis and thermal stability characterization of ADT. (a, b) The facile synthesis of ADT as a white crystalline solid in a good yield; (c) the DSC trace and (d) the TGA trace of ADT.

show good thermal stability, low explosibility and convenience in the isolation of diazo products. However, the starting materials for the synthesis of ADM reagents are relatively expensive, sensitive to moisture and difficult to handle,17-18 which limits the application of these highly efficient diazotransfer reagents. Therefore, the development of novel diazotransfer reagent that is safe, efficient and stable is strongly demanded. The new reagent is preferably stable solid at room temperature and can be easily prepared from low-cost and convenient starting materials.

ACS Paragon Plus Environment

The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Herein, we report 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT, compound 1) as an intrinsically safe, highly efficient and shelf-stable solid diazo-transfer reagent (Figure 1). Through a two-step procedure modified from Kayama’s synthesis procedure,19 ADT can be facilely synthesized as white crystalline solid in 77% total yield from low-cost and convenient starting materials: cyanuric chloride, sodium azide and methanol.19 Results and Discussion The structure of ADT in solution and in solid state has been characterized by using NMR, IR and XRD (see SI for details). The strong and sharp peak at 2143 cm-1 in IR spectrum indicates that ADT exists in the azido form in solid state. The thermal stability of ADT has been characterized by using DSC and TGA. There are two endothermal peaks on the DSC trace at 84.7 and 174.2 oC (Figure 1c), which are corresponding to the melting and thermal decomposition of ADT (Figure 1d), respectively. The safety issues of most of diazo-transfer reagents are mainly due to their fast exothermal decomposition processes.8 In contrast, the endothermal decomposition of ADT (∆H = 30.3 kJ mol-1) implies that ADT could be an intrinsically safe and nonexplosive compound. Indeed, the safety of ADT is further examined by BAM friction test and BAM fall hammer impact test (see SI for details), which demonstrate that ADT is insensitive upon the highest friction loading (360 N) and the highest impact energy (100 J) under standard test conditions. On the other hand, with inorganic solid base as the catalyst, ADT reacts with active methylene compounds to give stabilized diazo compounds in excellent yields within several minutes at room temperature. In addition, ADT crystalline solid is very stable upon long-term storage, whose reactivity remains unchanged after stored for >1 year under air at room temperature. The lifetime of ADT is much better than most of other diazo-transfer reagents, which is typically within several weeks.8 We began our study by testing the reaction between ethyl acetoacetate 2a and ADT in DMF at 25 oC (Table 1, entry 7). The corresponding diazo compound 3a was obtained after 1 h reaction with a 48% NMR yield using 40 mol% trimethylamine as the base. There was also ~40% yield of triazole product from 2a and ADT, as reported previously.20-21 Since the polarity of solvent is known to affect diazo-transfer reactions,8 we explored the effect of solvent using 2a /ADT reaction as a model system (Table 1). In low polarity solvents with polarity index P 1 year rt= room temperature; p-CBSA= 4-carboxybenzenesulfonyl azide; PS-SO2N3= polystyrene-supported benzenesulfonyl azide; pABSA= 4-acetamidobenzenesulfonyl azide; IMSA•HCl = imidazole-1-sulfonyl azide hydrochloride; ILSSA= ionic liquidsupported sulfonyl azide; ADMP= 2-azide-1,3-dimethylimidazolinium hexafluorophosphate.

Page 4 of 7

as the base, 1-diazoindene has been facilely prepared in a good yield (70%) (Table 3, entry 14). The reaction between indene and ADT is completed in 3 min at 25 oC, which minimizes the decomposition of the unstable 1-diazoindene and achieves this good yield. On the other hand, non-active ethylene compounds could not react with ADT to give diazo products (entry 15-17) even after 90 min reaction. For entry 16, only a small amount of benzyl alcohol was detected, due to the hydrolysis of ester. The scalability of this diazo-transfer reaction was examined by conducting a gram-scale reaction of 2a and ADT (12 mmol ADT and 10 mmol 2a) at the same concentration, reactant ratio, solvent and temperature as the entry 1 in Table 3. The gram-scale reaction was completed in 2 min with a 90% isolation yield of 3a, indicating the good scalability of this diazotransfer reaction. In Table 4, representative diazo-transfer reagents are summarized and compared with ADT based on their reactions with ethyl acetoacetate 2a. Although most of these diazo-transfer reagents can provide high yield (> 80%) of diazo product 3a, the reaction with ADT is the fastest (2 min at RT), followed by ionic liquid-supported sulfonyl azide (3 min at RT)29 and ADMP (10 min at 0 oC).18 Other reagents, including the only two commercial available diazo-transfer reagents (4-aceta midobenzenesulfonyl azide and p-tosyl azide) require longer reaction time (up to several hours) to give diazo product 3a in good yields. It is noticeable that the lifetime of most of these reagents are limited within several weeks, including the highly efficient reagents ionic liquid-supported sulfonyl azide29 and ADMP18 (a hygroscopic salt). In contrast, ADT is a hydrophobic solid and does not absorb water in air. Figure S3 shows the comparison of the IR spectrum of a freshly prepared ADT solid sample and a one-year-old ADT solid sample stored at room temperature. These two IR spectra are almost identical, which indicates ADT remains stable during the >1 year storage in air at room temperature. The exceptional stability of ADT crystalline solid is probably due to the conjugation and stabilization effect of the triazine ring on the azide group.19 Conclusion We have developed an intrinsically safe, highly efficient and shelf-stable crystalline solid reagent ADT for diazo-transfer reaction of activate methylene compounds. ADT can be facilely synthesized from low-cost and convenient starting materials. With inorganic solid base as catalyst, the diazo-transfer reaction based on ADT gives various diazo compounds in excellent yields within several minutes at room temperature, making ADT a promising diazo-transfer reagent for quick preparation of diazo compounds. EXPERIMENTAL SECTION General Information. Reagents involved in experiments were commercially purchased and were used as received without further purification for the reactions. Proton nuclear magnetic resonance (1H NMR) and carbon nuclear magnetic resonance (13C NMR) spectroscopy were performed on a Bruker Advance 400M NMR spectrometers. Chemical shifts 1H NMR spectra are reported as in units of parts per million (ppm) downfield from SiMe4 (0.0) and relative to the signal of chloroform-d (J = 7.264, singlet). Multiplicities were given as: s (singlet); t (triplet); q (quartet) and m (multiplets). The number of protons (n) for a given resonance is indicated by nH. Coupling constants are reported as a J value in Hz. Carbon nuclear magnetic resonance spectra (13C NMR) are reported as in units

ACS Paragon Plus Environment

4

Page 5 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Organic Chemistry of parts per million (ppm) downfield from SiMe4 (0.0) and relative to the signal of chloroform-d (J = 77.03, triplet). Synthetic Procedures and Spectra Data of 2-Azido-4,6Dimethoxy-1,3,5-Triazine (ADT). Cyanuric chloride (1.00 g, 5.4 mmol), NaHCO3 (1.10 g, 13.0 mmol) and 8 mL MeOH were introduced to a round-bottom flask equipped with a magnetic stirring bar. The solution was stirred at 0 °C for 0.5 h. Then, the reaction mixture was allowed to warm back to room temperature stirring 1.5 h. After that, it was heated to 50 °C and stirred for additional 2.0 h. The reaction mixture was concentrated in vacuum. Then, the mixture extracted with DCM and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum to provide the crude product. The crude product was purified by flash column chromatography (n-hexane/EtOAc = 10:1) on silica gel to afford 2-chloro-4,6-dimethoxy-1,3,5-triazine (0.76 g, 4.3 mmol, 80% yield). If the reaction scale was tripled (with 3.0 gram of cyanuric chloride as starting material), the yield of ADT was 2.46 g (86% yield). 1H NMR (400 MHz, CDCl3): δ 4.08 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 172.7, 172.6, 56.1. 2-chloro-4,6-dimethoxy-1,3,5-triazine (0.76 g, 4.3 mmol) and 5 mL acetonitrile were introduced to a round-bottom flask equipped with a magnetic stirring bar. Sodium azide solution (4.7 mmol NaN3 in 2 mL H2O) was added to the stirring above-mentioned solution. Then, the reaction mixture was stirred at 35 °C for 2.5 h. The reaction mixture was concentrated in vacuum. Then, the mixture extracted with DCM and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum to provide the product ADT (0.75 g, 4.1 mmol, 96% yield) as white solid. ADT can by recrystallized by dissolving in hot benzene and crystallized by adding petroleum ether. 1H NMR (400 MHz, CDCl3): δ 4.05 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 173.2, 172.2, 55.6. General Procedures A for the Synthesis of diazo compounds (3a-3e). Ethyl acetoacetate 2a (0.0650 g, 0.5 mmol), NaHCO3 (0.0168 g, 0.2 mmol) and 2 mL DMSO were added to a 4 mL vial equipped with a magnetic stirring bar. ADT (0.1092 g, 0.6 mmol) was added the solution. The solution was stirred at 25 °C for 2 minutes (monitored by TLC). Then, the mixture extracted with DCM and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum. The residue was purified by flash column chromatography on silica gel to afford 3. General Procedures B for the Synthesis of diazo compounds (3f-3i). Ethyl benzoylacetate 2f (0.0961 g, 0.5 mmol), K2CO3 (0.0276 g, 0.2 mmol) and 2 mL DMSO were added to a 4 mL vial equipped with a magnetic stirring bar. ADT (0.1092 g, 0.6 mmol) was added the solution. The solution was stirred at 25 °C for 2 minutes (monitored by TLC). Then, the mixture extracted with EA and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum. The residue was purified by flash column chromatography on silica gel to afford 3. General Procedures C for the Synthesis of diazo compounds (3j). Ethyl phenylacetate 2j (0.0821 g, 0.5 mmol), KOH (0.0112 g, 0.2 mmol) and 2 mL DMSO were added to a 4 mL vial equipped with a magnetic stirring bar. ADT (0.1092 g, 0.6 mmol) was added the solution. The solution was stirred at 25 °C for 6 minutes (monitored by TLC). Then, the mixture extracted with EA and H2O. The combined organic extracts

were dried with sodium sulfate, filtered and concentrated in vacuum. The residue was purified by flash column chromatography on silica gel to afford 3j. General Procedures D for the Synthesis of diazo compounds (3k-3m). 1,3-cyclohexanedione 2k (0.0568 g, 0.5 mmol), KOAc (0.0202 g, 0.2 mmol) and 2 mL DMSO were added to a 4 mL vial equipped with a magnetic stirring bar. 1 (0.1092 g, 0.6 mmol) was added the solution. The solution was stirred at 25 °C for 2 minutes (monitored by TLC). Then, the mixture extracted with DCM and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum. The residue was purified by flash column chromatography on silica gel to afford 3. General Procedures E for the Synthesis of diazo compounds (3n). Indene 2n (0.0592 g, 0.5 mmol), KOAc (0.0205 g, 0.2 mmol) and 2 mL DMSO were added to a 4 mL vial equipped with a magnetic stirring bar. ADT (0.1092 g, 0.6 mmol) was added the solution. The solution was stirred at 25 °C for 3 minutes (monitored by TLC). Then, the mixture extracted with DCM and H2O. The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuum. The organic phases were combined, dried with Na2SO4 and concentrated under a reduced pressure of ca. 20 Torr at 30 °C to afford 3n. Ethyl-2-diazo-3-oxobutanoate (3a). (General Procedure A) pale yellow liquid, 0.0703 g, 90% yield. (Eluent: n-hexane /EtOAc = 10:1). 1H NMR (400 MHz, CDCl3): δ 4.31 (q, J=7.1 Hz, 2H), 2.49 (s, 3H), 1.34 (t, J=7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 190.3, 161.4, 61.4, 28.3, 14.3. Tert-butyl2-diazo-3-oxobutanoate (3b). (General Procedure A) yellow liquid, 0.0825 g, 90% yield. (Eluent: n-hexane/EtOAc = 10:1). 1H NMR (400 MHz, CDCl3): δ 2.45 (s, 3H), 1.53 (s, 9H). 13C NMR (100 MHz, CDCl3): δ 190.6, 160.6, 83.2, 28.3, 28.2. Methyl-2-diazo-3-oxohexanoate (3c). (General Procedure A) pale yellow liquid, 0.0754 g, 89% yield. (Eluent: n-hexane /EtOAc = 10:1). 1H NMR (400 MHz, CDCl3): δ 3.84 (s, 3H), 2.83 (t, J=7.4 Hz, 2H), 1.72–1.62 (m, 2H), 0.97 (t, J=7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 192.8, 161.8, 52.1, 42.2, 17.8, 13.7. 3-diazopentane-2,4-dione (3d). (General Procedure A) pale yellow liquid, 0.0485 g, 77% yield. (Eluent: n-hexane/EtOAc = 10:1). 1H NMR (400 MHz, CDCl3): δ 2.44 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 188.3, 28.5. 2-diazo-1-phenylbutane-1,3-dione (3e). (General Procedure A) white solid, 0.0840 g, 89% yield. (Eluent: n-hexane/EtOAc = 5:1). 1H NMR (400 MHz, CDCl3): δ 7.67–7.62 (m, 2H), 7.61– 7.56 (m, 1H), 7.52–7.48 (m, 2H), 2.58 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 190.9, 185.1, 137.3, 132.7, 128.9, 127.4, 29.3. Ethy-2-diazo-3-oxo-3-phenylpropanoate (3f). (General Procedure B) pale yellow liquid, 0.0958 g, 88% yield. (Eluent: nhexane/EtOAc = 5:1). 1H NMR (400 MHz, CDCl3): δ 7.63 (d, J=7.0 Hz, 2H), 7.53 (t, J=7.4 Hz, 1H), 7.43 (t, J=7.5 Hz, 2H), 4.25 (q, J=7.1 Hz, 2H), 1.26 (t, J=7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 186.9, 161.0, 137.1, 132.3, 128.4, 127.9, 61.6, 14.2. Ethyl-2-diazo-3-(4-nitrophenyl)-3-oxopropanoate (3g). (General Procedure B) pale yellow liquid, 0.1014 g, 77% yield. (Eluent: n-hexane/EtOAc = 4:1). 1H NMR (400 MHz, CDCl3): δ 8.34–8.21 (m, 2H), 7.80–7.68 (m, 2H), 4.25 (q, J=7.1 Hz, 2H), 1.27 (t, J=7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 185.6, 160.4, 149.6, 142.5, 129.3, 123.1, 62.0, 14.2.

ACS Paragon Plus Environment

5

The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Diethyl-2-diazomalonate (3h). (General Procedure B) yellow liquid, 0.0837 g, 90% yield. (Eluent: n-hexane/EtOAc = 5:1). 1 H NMR (400 MHz, CDCl3): δ 4.31 (q, J=7.1 Hz, 4H), 1.32 (t, J=7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ 161.1, 61.6, 14.4. Ethyl-2-diazo-2-(diethoxyphosphoryl)acetate (3i). (General Pr-ocedure B) pale yellow liquid, 0.1226 g, 98% yield. (Eluent: n-hexane/EtOAc = 3:1). 1H NMR (400 MHz, CDCl3): δ 4.34– 4.11 (m, 6H), 1.37 (t, J=7.1 Hz, 6H), 1.31 (t, J=7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl3): δ 163.5, 163.4, 63.7, 63.6, 61.7, 16.2, 16.1, 14.3. Ethyl-2-diazo-2-phenylacetate (3j). (General Procedure C) red liquid, 0.0876 g, 92% yield. (Eluent: n-hexane/EtOAc = 4:1). 1 H NMR (400 MHz, CDCl3): δ 7.50–7.47 (m, 2H), 7.42–7.34 (m, 2H), 7.22–7.14 (m, 1H), 4.34 (q, J= 7.1 Hz, 2H), 1.34 (t, J=7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 165.3, 128.9, 125.8, 125.7, 123.9, 61.0, 14.5. 2-diazocyclohexane-1,3-dione (3k). (General Procedure D) pale yellow liquid, 0.0622 g, 90% yield. 1H NMR (400 MHz, CDCl3): δ 2.55 (t, J=8.0 Hz, 4H), 2.03 (m, (Eluent: n-hexane /EtOAc = 5:1).2H). 13C NMR (100 MHz, CDCl3): δ 190.5, 36.9, 18.6. 2-diazocyclopentane-1,3-dione (3l). (General Procedure D) yellow liquid, 0.0552 g, 89% yield. (Eluent: n-hexane/EtOAc = 4:1). 1H NMR (400 MHz, CDCl3): δ 2.75 (s, 4H). 13C NMR (100 MHz, CDCl3): δ 193.0, 33.9. 2-diazo-5,5-dimethylcyclohexane-1,3-dione (3m). (General Procedure D) white solid, 0.0764 g, 92% yield. (Eluent: nhexane/EtOAc = 3:1). 1H NMR (400 MHz, CDCl3): δ 2.42(s, 4H), 1.10(s, 6H). 13C NMR (100 MHz, CDCl3): δ 190.0, 50.6, 31.2, 28.5. 1-diazoindene (3n). (General Procedure E) red solid, 0.0498 g, 70% yield. 1H NMR (400 MHz, CDCl3): δ 7.56-7.53 (m, 1H), 7.47–7.45 (m, 1H), 7.21–7.19 (m, 2H), 7.02 (d, J=8.0 Hz, 1H), 6.37 (d, J=8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 135.3, 133.5, 124.1, 123.0, 122.7, 120.1, 118.7, 116.9.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. IR, XRD, DSC and TGA data of ADT. BAM friction and impact tests of ADT. 1H and 13C spectra of all compounds (PDF)

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21474094, 21722406) and the Fundamental Research Funds for the Central Universities (WK2060200025).

REFERENCES (1) Dolye, M. P.; Duffy, R.; Ratnikov, M.; Zhou, L., Catalytic Carbene Insertion into C-H Bonds. Chem. Rev. 2010, 110, 704-724. (2) Zhao, X.; Zhang, Y.; Wang, J. B., Recent developments in coppercatalyzed reactions of diazo compounds. Chem. Commun. 2012, 48 (82), 10162-10173.

Page 6 of 7

(3) Ford, A.; Miel, H.; Ring, A.; Slattery, C. N.; Maguire, A. R.; McKervey, M. A., Modern Organic Synthesis with alphaDiazocarbonyl Compounds. Chem. Rev. 2015, 115 (18), 9981-10080. (4) Xia, Y.; Qiu, D.; Wang, J. B., Transition-Metal-Catalyzed CrossCouplings through Carbene Migratory Insertion. Chem. Rev. 2017, 117 (23), 13810-13889. (5) He, H. Y.; Ding, W. D.; Bernan, V. S.; Richardson, A. D.; Ireland, C. M.; Greenstein, M.; Ellestad, G. A.; Carter, G. T., Lomaiviticins A and B, Potent Antitumor Antibiotics from Micromonospora lomaivitiensis. J. Am. Chem. Soc. 2001, 123, 5362-5363. (6) Köpke, T.; Zaleski, J. M., Diazo-Containing Molecular Constructs as Potential Anticancer Agents: From Diazo[b]fluorene Natural Products to Photoactivatable Diazo-Oxochlorins. Anti-Cancer Agent in Med. Chem. 2008, 8, 292-304. (7) Nawrat, C. C.; Moody, C. J., Natural products containing a diazo group. Nat. Prod. Rep. 2011, 28 (8), 1426-1444. (8) Maas, G., New syntheses of diazo compounds. Angew. Chem. Int. Edit. 2009, 48 (44), 8186-8195. (9) Mix, K. A.; Aronoff, M. R.; Raines, R. T., Diazo Compounds: Versatile Tools for Chemical Biology. ACS Chem. Biol. 2016, 11 (12), 3233-3244. (10) Regitz, M., New Methods of Preparative Organic Chemistry. Transfer of Diazo Groups. Angew. Chem. Int. Edit. 1976, 6, 733-734. (11) Taber, D. F.; Ruckle, R. E.; Jr.; Hennessy, M. J., Mesyl Azide: A Superior Reagent for Diazo Transfer. J. Org. Chem. 1986, 51, 40774078. (12) Hazen, G. G.; Weinstock, L. M.; Connell, R.; Bollinger, F. W., A Safer Diazotransfer Reagent. Synth. Commun. 1981, 11 (12), 947-956. (13) Green, G. M.; Peet, N. P.; Metz, W. A., Polystyrene-Supported Benzenesulfonyl Azide: A Diazo Transfer Reagent That Is Both Efficient and Safe. J. Org. Chem. 2001, 66, 2509-2511. (14) Goddard-Borger, E. D.; Stick, R. V., An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent: Imidazole-1-sulfonyl Azide Hydrochloride. Org. Lett. 2007, 9, 3797-3800. (15) Katritzky, A. R.; El Khatib, M.; Bol'shakov, O.; Khelashvili, L.; Steel, P. J., Benzotriazol-1-yl-sulfonyl azide for diazotransfer and preparation of azidoacylbenzotriazoles. J. Org. Chem. 2010, 75 (19), 6532-6539. (16) Ye, H.; Liu, R. H.; Li, D. M.; Liu, Y. H.; Yuan, H. X.; Guo, W. K.; Zhou, L. F.; Cao, X. F.; Tian, H. Q.; Shen, J.; Wang, P. G., A Safe and Facile Route to Imidazole-1-sulfonyl Azide as a Diazo transfer Reagent. Org. Lett. 2013, 15, 18-21. (17) Kitamura, M.; Tashiro, N.; Okauchi, T., 2-Azido-1,3-dimethyl imidazolinium Chloride: An Efficient Diazo Transfer Reagent for 1,3Dicarbonyl Compounds. Synlett 2009, 2943-2944. (18) Kitamura, M., Azidoimidazolinium Salts: Safe and Efficient Diazo-transfer Reagents and Unique Azido-donors. Chem. Rec. 2017, 17, 653-666. (19) Kayama, R.; Hasunuma, S.; Sekiguch.S; Matsui, K., Thermal Reactions of Azido-1,3,5-Triazines. Bulletin of the Chem. Soc. 1974, 47 (11), 2825-2829. (20) Mikhailychenko, S. N.; Chesniuk, A. A.; Koniushkin, L. D.; Firgang, S. I.; Zaplishny, V. N., Derivatives of sym-triazine. 3. Synthesis and some conversions of monoazides of the triazine series. Chemistry of Heterocyclic Compounds 2004, 40 (9), 1162-1168. (21) Mikhaylichenko, S.; Veloso, A.; Patel, K.; Zaplishny, V., Synthesis and structure of new 1, 2, 3-triazolyl substituted 1, 3, 5-triazines. European Journal of Chemistry 2012, 3 (1), 1-9 (22) Keipour, H.; Jalba, A.; Delage-Laurin, L.; Ollevier, T., CopperCatalyzed Carbenoid Insertion Reactions of alpha-Diazoesters and alpha-Diazoketones into Si-H and S-H Bonds. J. Org. Chem. 2017, 82 (6), 3000-3010. (23) Rewicki, D.; Tuchsche.C, 1-Diazoindene and Spiro[Indene-1,7'Norcaradiene]. Angew. Chem. Int. Edit. 1972, 11 (1), 44-45. (24) Pandit, R. P.; Kim, S. H.; Lee, Y. R., Iron ‐ Catalyzed Annulation of 1, 2-Diamines and Diazodicarbonyls for Diverse and Polyfunctionalized Quinoxalines, Pyrazines, and Benzoquinoxalines in Water. Adv. Synth. Catal. 2016, 358, 3586-3599. (25) Chiara, J. L.; Su á rez, J. R., Synthesis of α-Diazo Carbonyl Compounds with the Shelf-Stable Diazo Transfer Reagent Nona fluorobutanesulfonyl Azide. Adv. Synth. Catal. 2011, 353, 575-579.

ACS Paragon Plus Environment

6

Page 7 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Organic Chemistry (26) Lee., J. C.; Yuk, J. Y., An improved and efficient method for diazo transfer reaction of active methylene compounds. Synth. Commun. 1995, 25, 1511-1515. (27) Ye, F.; Wang, C. P.; Zhang, Y.; Wang, J. B., Synthesis of aryldiazoacetates through palladium(0)-catalyzed deacylative crosscoupling of aryl iodides with acyldiazoacetates. Angew. Chem. Int. Ed. 2014, 53 (43), 11625-11628. (28) Fischer, N.; Goddard-Borger, E. D.; Greiner, R.; Klapötke, T. M.; Skelton, B. W.; Stierstorfer, J., Sensitivities of some imidazole-1sulfonyl azide salts. J. Org. Chem. 2012, 77 (4), 1760-1764. (29) Muthyala, M. K.; Choudhary, S.; Kumar, A., Synthesis of ionic liquid-supported sulfonyl azide and its application in diazotransfer reaction. J. Org. Chem. 2012, 77 (19), 8787-8791.

ACS Paragon Plus Environment

7