Iodine(V) Reagents in Organic Synthesis. Part 2. Access to Complex Molecular Architectures via Dess−Martin Periodinane-Generated <i>o</i>-Imidoquinones

Nicolaou, K. C.; Sugita, Kazuyuki; Ps, Baran; Yl, Zhong

doi:10.1021/ja012125p

Cited by 118 publications

(64 citation statements)

References 24 publications

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“…23 Some of these new reactions and enabling synthetic technologies are described in detail in the following papers. [24][25][26][27] …”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of the CP-Molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). 3. Completion and Synthesis of Advanced Analogues

Nicolaou

et al. 2002

J. Am. Chem. Soc.

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The completion of the total syntheses of the CP-molecules is reported. Several strategies and tactics, including the use of amide-based protecting groups for the homologated C-29 carboxylic acid and the use of an internal pyran protecting group scheme, are discussed. The endeavors leading to the design of new methods for the homologation of hindered aldehydes and to the isolation of a polycyclic byproduct (23), which inspired the development of a new series of reactions based on iodine(V) reagents, are described. In addition, the discovery and development of the LiOH-mediated conversion of CP-263,114 (1) to CP-225,917 (2) is described, and a mechanistic rationale is presented. Finally, a synthetic route to complex analogues of the CP-molecules harboring a maleimide moiety in place of the maleic anhydride is presented.

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“…23 Some of these new reactions and enabling synthetic technologies are described in detail in the following papers. [24][25][26][27] …”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of the CP-Molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). 3. Completion and Synthesis of Advanced Analogues

Nicolaou

et al. 2002

J. Am. Chem. Soc.

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“…[64] Iodine(V) reagents: Iodine(V) has also been used to effect the direct oxyamination of olefins by Nicolaou et al [65] In this procedure, the exposure of N-arylamides 101 to DessMartin periodinane (DMP) delivered iso-imidoquinone intermediates 102, which underwent [4 + 2] Diels-Alder reactions with a range of electron-rich alkenes to afford the desired 2-amilides 103 (Scheme 43). [66] This methodology was applied in the core synthesis of various complex natural products such as elisabethin A and pseudopterosin A (Figure 3).…”

Section: Metal-free Oxidation Protocolsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

262

116

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1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.

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“…8 In our experiment to improve the yield of the product 3c, the commercially available oxidizing reagent Dess-Martin was used. 17 As shown in Table 1, more substantial increase of the yield was found in toluene as the reaction medium.…”

Section: Papermentioning

confidence: 82%

“…Compound was prepared from the corresponding heterocyclic salts, the bases were generated in situ by addition of Et 3 N. b Dess-Martin reagent was used as the oxidizing agent 17. …”

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confidence: 99%

One-Pot Synthesis of 6′-Amino-Substituted Spirooxazines

Koshkin¹,

Lokshin²,

Samat³

et al. 2005

Synthesis

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A one-pot synthesis of 6¢-amino-substituted spiroindolinonaphth[2,1-b] [1,4]oxazines is developed through the condensation of 2-methylene-1,3,3-trimethylindoline derivatives and 1-amino-2-naphthol in the presence of different secondary amines and oxidizing agents using methanol or toluene as the solvent. The main advantage of the method is its simplicity, and starting from readily accessible reagents, it allows the preparation of amino derivatives of spironaphthoxazine with good yields under mild reaction conditions.Spirooxazines have UV activation properties and thermal bleaching properties that are convenient for practical applications. 1-5 By now, the widely applied procedures for the synthesis of spirooxazines consist in the condensation of nitrogen-containing heterocycles with hydroxynitroso compounds. 3 Unfortunately, this method affords spirooxazines in low yields, even if optimization of experimental conditions allowed to improve it in some cases. 3,6 The spirooxazine molecule can be constructed also by using 1-amino-2-naphthol as the starting material. [7][8][9][10][11][12] Most of the structural modifications of the oxazine fragment in spiro compounds are based on the substitution on the naphthalene ring. The required group is most commonly introduced into this fragment already in the preparation of the starting 1-nitroso-2-naphthol. Rickwood and co-workers used some secondary amines as nucleophiles for the preparation of 6¢-amino-substituted spironaphthoxazines. [13][14][15][16] It was assumed that the reaction involves the nucleophilic addition of secondary amine at position 4 of the quinone oxime tautomer of 1-nitroso-2-naphthol. Subsequent oxidation of intermediate can occur under the action of a second 1-nitroso-2-naphthol molecule, which partially accounts for the low yield.In this paper we describe the synthesis of the 6¢-aminosubsituted spirooxazines by one-pot condensation of 1-amino-2-naphthol with substituted 2-methyleneindolines in the presence of different secondary amines and oxidizing agent using methanol or toluene as the solvent (Scheme 1). To evaluate the general validity of the method and to show its advantages and limitations we varied the substituents in indoline molecules 1a-d and used different secondary cyclic amines 2a-d.Our experiments showed that alicyclic/aliphatic secondary amines did not participate in the condensation reaction. In the presence of diethylamine or bis(2-methoxyethyloxy)amine the condensation of 1a with 1-amino-2-naphthol results in the formation of unsubstituted spiroindolinonaphth[2,1-b][1,4]oxazine. In contrast, the method was successfully applied for the preparation of spirooxazines 3a-c, 4a, 5, and 6 with cyclic amine substitScheme 1 N R 2

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Iodine(V) Reagents in Organic Synthesis. Part 2. Access to Complex Molecular Architectures via Dess−Martin Periodinane-Generated o-Imidoquinones

Cited by 118 publications

References 24 publications

Total Synthesis of the CP-Molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). 3. Completion and Synthesis of Advanced Analogues

Total Synthesis of the CP-Molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). 3. Completion and Synthesis of Advanced Analogues

Recent Developments in Methodology for the Direct Oxyamination of Olefins

One-Pot Synthesis of 6′-Amino-Substituted Spirooxazines

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