Selective reactions of azide-substituted .alpha.-diazo amides with olefins and alcohols using rhodium(II) catalysts

Jeganathan, Alwarsamy; Richardson, Stewart K.; Mani, R. S.; Haley, Boyd E.; Watt, David S.

doi:10.1021/jo00376a057

Cited by 24 publications

(10 citation statements)

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“…The obtained azido diazo materials are highly versatile, and 2a was chemoselectively conjugated, as shown in Scheme . Staudinger–Bertozzi ligation , with phosphine 7 produced azido-selectively conjugated diazo compound 8 .…”

Section: Resultsmentioning

confidence: 99%

“…The moderate yield of 6b is following those of monoazido ketones (Scheme 2), and the use of a weak base converted the site-selective keto-azido group in the presence of other two azido groups. The obtained azido diazo materials are highly versatile, 28 and 2a was chemoselectively conjugated, as shown in Scheme 4.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…2-Diazo-1-(4-methoxyphenyl)ethan-1-one (4j).. 19b,25a A total of 13.2 mg of 4j (75%) was obtained from azide 3j (19.1 mg, 0.10 mmol), tosyl hydrazide (93.9 mg, 0.50 mmol, 5.0 equiv), and pyrrolidine (21.0 μL, 0.25 mmol, 2.5 equiv) in DMSO (0.5 mL, 0.2 M) for 3 h followed by neutral silica gel chromatography (hexane/ethyl acetate = 10/1 to 6/1): pale yellow solid; R f value 0.50 (hexane/ethyl acetate = 1/1); mp 75−76 °C; IR (NaCl, neat) ν max 3099,2115,1611,1590,1567,1388, 1372 cm −1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 7.74 (d, 2H, J = 9.0 Hz), 6.93 (d, 2H, J = 9.0 Hz), 5.85 (s, 1H), 3.87 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ 185. 2, 163.2, 129.4, 128.7, 113.8, 55.4, 53.5; LRMS (EI, M = C 9 H 8 N 2 O 2 ) m/z 176 (79%, M + ), 135 (100), 120 (28), 91 (35), 77 (52); HRMS (EI) calcd for C 9 H 8 N 2 O 2 (M + ) 176.0586, found 176.0589. 1-(4-Bromophenyl)-2-diazoethan-1-one (4k).. 19b,25a A total of 13.0 mg of 4k (58%) was obtained from the reaction with azide 3k (17.4 mg, 0.10 mmol), tosyl hydrazide (93.1 mg, 0.50 mmol, 5.0 equiv), and pyrrolidine (21.0 μL, 0.25 mmol, 2.5 equiv) in DMSO (0.5 mL, 0.2 M) for 0.5 h followed by neutral silica gel chromatography (hexane/ ethyl acetate = 10/1): pale yellow solid; R f value 0.37 (hexane/ethyl acetate = 3/1); mp 110−111 °C; IR (KBr, disc) ν max 3115, 2118, 1608, 1590, 1401, 1379, 1070 cm −1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 7.63 (d, 2H, J = 8.5 Hz), 7.59 (d, 2H, J = 8.5 Hz), 5.88 (s, 1H); 13 C NMR (126 MHz, CDCl 3 ) δ 185.1, 135.3, 131.9, 128.2, 127.6, 54.4; LRMS (EI, M = C 8 H 5 BrN 2 O) m/z 226 (42%, M + of 81 Br), 224 (42, M + of 79 Br), 185 (55), 183 (56), 89 (100)…”

Section: N-benzyl-2-diazo-n-(4-vinylphenyl)acetamide (4g)mentioning

confidence: 99%

“…Compound 2d: pale yellow solid; R f value 0.37 (hexane/ethyl acetate = 1/1); mp 65− 66 °C; IR (NaCl, neat) ν max 2105, 1671, 1602, 1361 cm −1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 7.74 (d, 2H, J = 8.0 Hz), 7.28−7.26 (m, 3H), 7.17 (dd, 2H, J = 4.0, 3.5 Hz), 7.06 (d, 2H, J = 7.5 Hz), 5.87 (s, 1H), 4.91 (s, 2H), 3.60 (s, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 184.7, 166. 9, 144.0, 136.6, 136.0, 128.9, 128.6, 128.5, 128.3, 127.9, 54.8, 53.3, 50.9; LRMS (EI, M = C 17 H 14 N 6 O 2 ) m/z 334 (18%, M + ), 250 (21), 222 (27), 187 (28), 174 (62), 118 (71), 91 (100); HRMS (EI) calcd for C 17 H 14 N 6 O 2 (M + ) 334.1178, found 334.1177.…”

Section: N-(3-(azidomethyl)phenyl)-n-benzyl-2-diazoacetamide (2c)mentioning

confidence: 99%

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Site-Selective Conversion of Azido Groups at Carbonyl α-Positions to Diazo Groups in Diazido and Triazido Compounds

et al. 2018

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This paper reports on the selective conversion of alkyl azido groups at the carbonyl α-position to diazo compounds. Through β-elimination of dinitrogen, followed by hydrazone formation/decomposition, α-azidocarbonyl moieties were transformed into α-diazo carbonyl groups in one step. As these reaction conditions do not involve aryl or general alkyl azides, site-selective conversions of di- and triazides were achieved. Through this method, the successive site-selective conjugation of the triazido molecule with three different components is demonstrated.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: N-benzyl-2-diazo-n-(4-vinylphenyl)acetamide (4g)mentioning

confidence: 99%

Section: N-(3-(azidomethyl)phenyl)-n-benzyl-2-diazoacetamide (2c)mentioning

confidence: 99%

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Site-Selective Conversion of Azido Groups at Carbonyl α-Positions to Diazo Groups in Diazido and Triazido Compounds

et al. 2018

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“…This DAE derivative was synthesized according to the procedure previously reported for N ‐phenyl‐ α ‐[( tert ‐butoxycarbonyl)amino]acetamide 17. A portion of the amino‐nitro‐substituted precursor 8 o (109 mg, 206 μmol),7c BOC‐protected glycine (36 mg, 206 μmol), and DCC (44 mg, 212 μmol) were stirred in anhydrous dichloromethane (2 mL) at 25 °C for 5 h in an argon atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Tuning the Redox Properties of Photochromic Diarylethenes by Introducing Electron‐Withdrawing Substituents

Berberich

Würthner

2013

Asian J Org Chem

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A series of seven photochromic diarylethenes (DAEs) with various electron‐withdrawing substituents and their respective closed‐form isomers (DAEC) were synthesized and the optical and redox properties of these photochromes were investigated by UV/vis absorption spectroscopy and cyclic voltammetry. Our comparative studies with these DAEs revealed that the absorption properties of the closed forms and the redox potentials of the open and closed isomers appreciably depend on the number and nature of the electron‐withdrawing groups introduced into the DAE unit. The DAE derivatives can be photochemically switched between two different states with different redox properties. Most prominently, photochrome 3 with two nitro groups has a first reduction potential for the open form 3 o of −1.51 V and for the corresponding closed form 3 c of −0.96 V, and, therefore, is particularly interesting as switchable electron‐acceptor moiety in photochromic systems.

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Intermolecular Metal‐Catalyzed Carbenoid Cyclopropanations

2001

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The metal‐catalyzed decomposition of diazo compounds in the presence of alkenes is a well‐established reaction. Since the original Organic Reactions review on the reaction of ethyl diazoacetate with alkenes and aromatic compounds in 1970, several new developments have revolutionized this area of chemistry. Most notably, major advances have been made in catalyst design such that highly chemoselective, diastereoselective and enantioselective carbenoid transformations can now be achieved. Furthermore, it has been recognized that a wide array of carbenoid structures can be utilized in this chemistry, leading to a broad range of synthetic applications. This chapter comprises coverage of the metal‐catalyzed intermolecular cyclopropanations of diazo compounds containing at least one adjacent electron‐withdrawing group. The coverage of diazoacetate chemistry will be limited to material since 1970 because the previous Organic Reactions review covers the earlier literature. The alkene component is limited to alkenes, dienes, furans, and pyrroles because these are the systems that have resulted in the greatest developments since the 1970 review. Metal‐carbenoid intermediates derived from diazo compounds undergo a variety of useful reactions, including cyclopropanation, insertion, and ylide formation. In recent years several excellent reviews have appeared on various aspects of this chemistry. Three recent reviews have focused on asymmetric intermolecular cyclopropanations. Several books and reviews on carbenoid chemistry have major sections on intermolecular cyclopropanations. Because of the historical central prominence of carbenoids derived from diazoacetates, most reviews have tended to focus on this class of carbenoids. In this chapter, a comparison is presented of the chemical differences that exist among the major classes of carbenoids that contain adjacent electron‐withdrawing groups. The extensive nature of the topic precludes coverage of related reactions such as the metal‐catalyzed decomposition of diazoalkanes, phenyldiazoalkanes, or vinyldiazoalkanes that lack adjacent electron‐withdrawing functionality. Other cyclopropanation reactions such as the Simmons‐Smith reaction, photochemical or thermal decomposition of diazo compounds in the presence of alkenes, and cyclopropanation using stoichiometric metal carbenes are not covered.

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Selective reactions of azide-substituted .alpha.-diazo amides with olefins and alcohols using rhodium(II) catalysts

Cited by 24 publications

References 0 publications

Site-Selective Conversion of Azido Groups at Carbonyl α-Positions to Diazo Groups in Diazido and Triazido Compounds

Site-Selective Conversion of Azido Groups at Carbonyl α-Positions to Diazo Groups in Diazido and Triazido Compounds

Tuning the Redox Properties of Photochromic Diarylethenes by Introducing Electron‐Withdrawing Substituents

Intermolecular Metal‐Catalyzed Carbenoid Cyclopropanations

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