Total synthesis of newbouldine via reductive N–N bond formation

Pangerl, Michael; Hughes, Chambers C.; Trauner, Dirk

doi:10.1016/j.tet.2010.05.085

Cited by 15 publications

(8 citation statements)

References 29 publications

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“…20,21 In contrast, the first synthesis of the pyrazoline congener (–)-newbouldine was reported only recently by Trauner, using reductive cyclization of a nitroalkyl-substituted pyrrolidine and confirming the racemic nature of this natural product. 22 …”

Section: Resultsmentioning

confidence: 99%

“…20,21 In contrast, the rst synthesis of the pyrazoline congener (À)-newbouldine was reported only recently by Trauner, using reductive cyclization of a nitroalkylsubstituted pyrrolidine and conrming the racemic nature of this natural product. 22 Thus, we synthesized the tetrazole substrate E-22 by LiAlH 4 reduction of acid 21 (ref. 23) followed by Mitsunobu reaction of the resulting alcohol with 5-(methylthio)tetrazole (1) (Fig.…”

Section: Total Synthesis Of (Ae)-newbouline and Withasomninementioning

confidence: 99%

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5-(Methylthio)tetrazoles as versatile synthons in the stereoselective synthesis of polycyclic pyrazolines via photoinduced intramolecular nitrile imine–alkene 1,3-dipolar cycloaddition

2014

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A key thioether substituent in readily accessible 2-alkyl-5-(methylthio)tetrazoles enables facile photoinduced denitrogenation and intramolecular nitrile imine 1,3-dipolar cycloaddition to afford a wide range of polycyclic pyrazoline products with excellent diastereoselectivity. The methylthio group red-shifts the UV absorbance of the tetrazole, obviating the requirement in all previous substrate systems for at least one aryl substituent, and can subsequently be converted into a variety of other functionalities. This synthetic platform has been applied to the concise total syntheses of the alkaloid natural products (±)-newbouldine and withasomnine.

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Section: Resultsmentioning

confidence: 99%

Section: Total Synthesis Of (Ae)-newbouline and Withasomninementioning

confidence: 99%

5-(Methylthio)tetrazoles as versatile synthons in the stereoselective synthesis of polycyclic pyrazolines via photoinduced intramolecular nitrile imine–alkene 1,3-dipolar cycloaddition

2014

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“…The N-N bond-formation reaction, via reduction of a nitro compound, was applied in the total synthesis of (-)newbouldine (13) by Trauner and co-workers in 2010 (Scheme 9). 23 TiCl 3 was used as a reductant to remove oxygen from the nitro group. The reaction under basic conditions afforded (-)-newbouldine (13) after elimination of a titanium(IV) oxo species.…”

Section: Scheme 4 Cyclization Of Oximes By Intramolecular Nucleophilimentioning

confidence: 99%

Recent Advances in Nitrogen–Nitrogen Bond Formation

Guo

2017

Synthesis

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Over the last decade, N–N bond formation as a synthetic strategy has emerged as a powerful key step in the construction of highly valuable heterocycles from easily obtained materials. This review focuses on recent methods used to build N–N bonds, classified by intra- and intermolecular reactions with various types of N–X (O, C, N, H) bond cleavage.1 I ntroduction2 Intramolecular N–N Bond Formation2.1 Cleavage of N–O Bonds2.2 Cleavage of N–C Bonds2.3 Cleavage of N–N Bonds2.4 Cleavage of N–H Bonds2.4.1 Construction of Pyrazole Derivatives2.4.2 Construction of Triazole Derivatives2.4.3 Construction of Indazole and Pyrazoline Derivatives2.4.4 Construction of Other N–N Bond Derivatives3 Intermolecular N–N Bond Formation4 Conclusion

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“…Finally, to further illustrate the utility of this method, we were able to apply the N–N cyclization strategy process to the synthesis of (−)-newbouldine ( I ), an alkaloid possessing potent neurological effects (Scheme ). , Grignard reaction, Wittig reaction, and subsequent hydroboration–oxidation from the readily available proline precursor 12 proceeded in high yield to construct 13 ; azidation of 13 afforded the protected azidoamine 14 in 75% yield (dr = 1.5:1). After Boc deprotection, our N–N cyclization was utilized to construct the [5,5]-bicyclic framework and access (−)-newbouldine in 42% yield.…”

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confidence: 99%

Fe(III)-Catalyzed Aerobic Intramolecular N–N Coupling of Aliphatic Azides with Amines

et al. 2019

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An Fe(III)-catalyzed intramolecular N–N coupling of aliphatic azidoamines that forms diverse five- and six-membered semisaturated diazoheterocycles using air as an oxidant is reported, providing an alternative to hydrazine-based methods. Mechanistic studies suggest that a N-radical induced intramolecular homolytic substitution (SH2) is involved in ring closure. The power of this N–N bond-forming method is also demonstrated by using it as the final step in a total synthesis of (−)-newbouldine.

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Total synthesis of newbouldine via reductive N–N bond formation

Cited by 15 publications

References 29 publications

5-(Methylthio)tetrazoles as versatile synthons in the stereoselective synthesis of polycyclic pyrazolines via photoinduced intramolecular nitrile imine–alkene 1,3-dipolar cycloaddition

5-(Methylthio)tetrazoles as versatile synthons in the stereoselective synthesis of polycyclic pyrazolines via photoinduced intramolecular nitrile imine–alkene 1,3-dipolar cycloaddition

Recent Advances in Nitrogen–Nitrogen Bond Formation

Fe(III)-Catalyzed Aerobic Intramolecular N–N Coupling of Aliphatic Azides with Amines

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