Stereochemical Aspects of the Iodine(III)-Mediated Aziridination Reaction of Some Cyclic Allylic Carbamates

Padwa, Albert; Stengel, Thomas

doi:10.1021/ol0259490

Cited by 108 publications

(26 citation statements)

References 18 publications

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“…[35] Although further experiments extended the scope of the oxygen source to include alcohols, it was found that the high diastereoselectivity of the reaction was limited to the 3-indolyl carbamates; both 2-indolyl carbamates 35 and benzofuran derivatives 36 gave mixtures of cis and trans oxyamination products (Scheme 15). [36] Attempts to effect this transformation with other classes of alkene also failed, as the aziridine species could not be opened by oxygen nucleophiles under the reaction conditions.…”

Section: Rhodium-catalysed Reactionsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

263

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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Section: Rhodium-catalysed Reactionsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

263

116

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“…Padwa has shown that rhodium-catalyzed oxidation of indolyl carbamate 67 employing either PhI(OAc) 2 or PhI=O follows a path similar to that of the d-allal carbamate (Scheme 17.26) [95]. In principle, indole attack of the putative rhodium-nitrene generates zwitterion 68, which is trapped subsequently by an exogenous nucleophile.…”

Section: Carbamate Estersmentioning

confidence: 99%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

105

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17 Rhodium(II)-Catalyzed Oxidative Amination 380 Scheme 17.1 Copper-catalyzed decomposition of arylsulfonyl azides. Scheme 17.2 Intramolecular C-H amination of an iminoiodinane. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 381 Scheme 17.3 Metal porphyrin-catalyzed allylic amination. Scheme 17.4 C-H amination by a radical-rebound mechanism. 17 Rhodium(II)-Catalyzed Oxidative Amination 382 Scheme 17.5 Rhodium-catalyzed N-atom transfer using NsN=IPh. Scheme 17.6 Stereospecific C-H amination under rhodium-catalyzed conditions. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 383 Scheme 17.7 Radical clock study of metallo-nitrene C-H insertion. Scheme 17.8 Intermolecular C-H insertion by chiral rhodium catalysts. 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 385 Scheme 17.11 Allylic and benzylic amination using PhI(OAc) 2 . 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 387 Tab. 17.1 C-H amination of 18 carbamate esters. Entry Substrate Product Entry Substrate Product 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 389 Scheme 17.14 Ketone formation by 28 alcohol-derived carbamates. 17.7 Enantioselective C-H Insertion with Sulfamate Esters 401 Scheme 17.29 Oxidative cyclization of unsaturated sulfonamides. Scheme 17.30 Preliminary investigations of asymmetric C-H amination. 17.11 Applications of C-H Amination in Synthesis 407 17.11 Applications of C-H Amination in Synthesis 409 Scheme 17.39 Asymmetric synthesis of (-)-tetrodotoxin. 17 Rhodium(II)-Catalyzed Oxidative Amination 410 Scheme 17.40 Nucleophilic ring opening of N-acylated oxathiazinanes. Scheme 17.41 Nickel-catalyzed cross-coupling of phenol-derived sulfamate esters.

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“…We speculate that the rhodium-catalyzed oxidative cyclization of an indol-3-ylmethanol carbamate 7 (Scheme 9, 15 → 16), which was postulated to involve nucleophilic attack of the indole on the nitrogen of a rhodium-nitrene complex, is a partial precedent for the present conversion. …”

Section: Methodsmentioning

confidence: 97%

The synthesis of 1,2,3,6,6a,7-hexahydro-7-methyl-5-imino-1H-pyrrolo[1,2-c]imidazolo[5,4-b]indole

Plá¹,

Mills²,

Joule³

et al. 2009

Arkivoc

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This paper is dedicated to Henk van der Plas who has for many years inspired heterocyclicchemists the world over with his innovative research, his impeccable standards and his charming personality propan-N-(2,2,2-trichloroethoxysulfonyl)guanidine was synthesized from 3-formyl-1-methylindole in six steps and subjected to conditions intended to convert the side-chain into a 2-iminotetrahydropyrimidine-containing product, of relevance to a possible synthesis of the aplicyanins. An alternative reaction course was observed, resulting in the formation of a new tetracyclic system. Abstract

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Stereochemical Aspects of the Iodine(III)-Mediated Aziridination Reaction of Some Cyclic Allylic Carbamates

Cited by 108 publications

References 18 publications

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Rhodium(II)‐Catalyzed Oxidative Amination

The synthesis of 1,2,3,6,6a,7-hexahydro-7-methyl-5-imino-1H-pyrrolo[1,2-c]imidazolo[5,4-b]indole

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