Conversion of aliphatic amides into amines with [I,I-bis(trifluoroacetoxy)iodo]benzene. 1. Scope of the reaction

Loudon, G. Marc; Radhakrishna, A. S.; Almond, Merrick R.; Blodgett, Jordan; Boutin, Rebecca

doi:10.1021/jo00196a031

Cited by 176 publications

(64 citation statements)

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“…This transformation has been described with DIB, 397 PIFA, 398,399 and HTIB. 400 An important feature of this rearrangement is the retention of configuration of the migrating…”

Section: Hofmann-type Rearrangementmentioning

confidence: 99%

“…401 The procedure described by Loudon and co-workers using PIFA in aqueous acetonitrile appears to be the most commonly employed in total synthesis of natural products. 398 Examples of applications are (±)-2-epi-validamine (Scheme 87), 402 pantocin B, 403,404 and (─)-platensimide A (Scheme 88). 299 An 66 application of this rearrangement in large scale has been reported using DIB.…”

Section: Hofmann-type Rearrangementmentioning

confidence: 99%

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Hypervalent iodine reagents in the total synthesis of natural products

2011

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“…This transformation has been described with DIB, 397 PIFA, 398,399 and HTIB. 400 An important feature of this rearrangement is the retention of configuration of the migrating…”

Section: Hofmann-type Rearrangementmentioning

confidence: 99%

Section: Hofmann-type Rearrangementmentioning

confidence: 99%

Hypervalent iodine reagents in the total synthesis of natural products

2011

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“…H-NMR (400 MHz) and 13 C-NMR (100 MHz) spectra were recorded on a JNM-ECA-400 NMR spectrometer in CDCl 3 or DMSO-d 6 (TMS as internal standard). FT-IR spectra were recorded on a Nicolet FT-IR 5700 spectrometer using KBr pellets.…”

Section: -8mentioning

confidence: 99%

Synthesis of [¹⁵N]t‐butylamine hydrochloride

Zhang

Lin

et al. 2010

Labelled Comp Radiopharmac

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Introduction t-Butylamine is a versatile and important building block for compounds with biological activities. Finasteride, a 5a-reductase inhibitor for use in treating acne, female hirsutism and benign prostatic hyperplasia, was prepared by the reaction of the carboxylate of 4-aza-5a-androst -1-ene-3-one with t-butylamine. 1It was also built into an apoptosis inhibitor, 2 an HIV protease inhibitor, 3 various antibotics 4 and nucleosides. 5 Moreover t-butylamine residues are commonly in adrenergic drugs to increase affinity for b-adrenoceptors. 6-8Here we describe an efficient synthesis of [15 N]t-butylamine hydrochloride, which can be used as biomarker for biologically active compounds containing this motif or incorporated in the synthesis of drug candidates for use as analytical internal standards or for metabolic studies. H-NMR (400 MHz) and 13 C-NMR (100 MHz) spectra were recorded on a JNM-ECA-400 NMR spectrometer in CDCl 3 or DMSO-d 6 (TMS as internal standard). FT-IR spectra were recorded on a Nicolet FT-IR 5700 spectrometer using KBr pellets. EI-MS Spectra were obtained with ZAB-HS spectrometer. : 3390, 3199, 2961, 2923, 2756, 1648, 1485, 1455, 1408, 1376, 1356, 1221, 1103, 863, 816, 732, 615 45 mmol) in DMF (8 mL), followed by the addition of a solution of NBS (0.48 g, 2.7 mmol) in DMF (2 mL) at room temperature under nitrogen. After reaction at this temperature for 30 h, the reaction mixture was poured into water and extracted with CH 2 Cl 2 (15 mL Â 3). The combined extracts were washed with water, saturated NaHCO 3 , dried over anhydrous magnesium sulfate and evaporated. The crude product was purified by flash chromatography (petroleum ether: ethyl 3341, 2969, 1713, 1498, 1454, 1394, 1365, 1266, 1210, 1072, 914, 776, 738, 696 Results and discussion

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“…Phenyliodine(III) bis(trifluoroacetate) (PIFA) was prepared according to the procedure reported by Loudon. 66 Solutions of sodium triacetoxyborohydride were prepared freshly by reacting sodium borohydride with acetic acid.…”

Section: Experimental Section Reagentsmentioning

confidence: 99%

Nitrenium Ion Azaspirocyclization—Spirodienone Cleavage: A New Synthetic Strategy for the Stereocontrolled Preparation of Highly Substituted Lactams and N‐Hydroxy Lactams.

Wardrop

Burge

2006

ChemInform

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Although 1,4-cyclohexadienes 2, obtained through the Birch reduction of arenes 1, have found widespread use as masked β-oxo carbonyl synthons 3, the possibility that 2,5-cyclohexadienones 5 might also be employed to the same end has been overlooked despite their ready availability. As part of our ongoing investigation of the synthetic chemistry of nitrenium ions, we have developed a novel and efficient strategy for the stereoselective preparation of di-and trisubstituted azetidinone, pyrrolidinone and piperidinone derivatives, which features the ozonolytic cleavage of azaspirocyclic 2,5-cyclohexadienones 12. For example, ozonolysis of spirodienone 12c in CH 2 Cl 2 and reductive workup with dimethyl sulfide generated unstable β-formyl ester 21 whereas cleavage in MeOH followed by reduction with thiourea led to hemiacetal 22. While both 21 and 22 partially decompose upon exposure to silica gel, they can be trapped in situ, with a variety of weakly basic nucleophiles, to usefully substituted products. The requisite spirodienone substrates are readily accessible through the nitrenium ion cyclization of alkyl ω-arylhydroxamates 10, proceeds with moderate to high diastereoselectivity.

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Conversion of aliphatic amides into amines with [I,I-bis(trifluoroacetoxy)iodo]benzene. 1. Scope of the reaction

Cited by 176 publications

References 0 publications

Hypervalent iodine reagents in the total synthesis of natural products

Hypervalent iodine reagents in the total synthesis of natural products

Synthesis of [¹⁵N]t‐butylamine hydrochloride

Nitrenium Ion Azaspirocyclization—Spirodienone Cleavage: A New Synthetic Strategy for the Stereocontrolled Preparation of Highly Substituted Lactams and N‐Hydroxy Lactams.

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Conversion of aliphatic amides into amines with [I,I-bis(trifluoroacetoxy)iodo]benzene. 1. Scope of the reaction

Cited by 176 publications

References 0 publications

Hypervalent iodine reagents in the total synthesis of natural products

Hypervalent iodine reagents in the total synthesis of natural products

Synthesis of [15N]t‐butylamine hydrochloride

Nitrenium Ion Azaspirocyclization—Spirodienone Cleavage: A New Synthetic Strategy for the Stereocontrolled Preparation of Highly Substituted Lactams and N‐Hydroxy Lactams.

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Synthesis of [¹⁵N]t‐butylamine hydrochloride