An Efficient Asymmetric Synthesis of Manzacidin C

Tran, Kristy; Lombardi, Pamela J.; Leighton, James L.

doi:10.1021/ol8011869

Cited by 57 publications

(23 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Scheme 52b) 354. Exposure of alkene 237 and hydrazone 238 to chiral silane R,R-B gave pyrazolidine 239, thus setting both stereocenters of the target molecule, including the ATA, in a single step.…”

mentioning

confidence: 99%

Synthetic approaches towards alkaloids bearing α-tertiary amines

et al. 2016

View full text Add to dashboard Cite

Alkaloids account for some of the most beautiful and biologically active natural products. Although they are usually classified along biosynthetic criteria, they can also be categorized according to certain structural motifs. Amongst these, the α-tertiary amine (ATA), i.e. a tetrasubstituted carbon atom surrounded by three carbons and one nitrogen, is particularly interesting. A limited number of methods have been described to access this functional group and fewer still are commonly used in synthesis. Herein, we review some approaches to asymmetrically access ATAs and provide an overview of alkaloid total syntheses where those have been employed.

show abstract

mentioning

confidence: 99%

Synthetic approaches towards alkaloids bearing α-tertiary amines

et al. 2016

View full text Add to dashboard Cite

show abstract

“…In their studies an Fe/αKG enzyme GriE, implicated in the biosynthesis of griselimycin from a Streptomyces strain [31], was found to possess relaxed substrate specificity and was adept at catalyzing the remote hydroxylation of 11 amino acids. The transformation could be employed on preparative scale with 8 in the truncated synthetic route to manzacidin C (five steps formal vs. 13 previous [32]), demonstrating the power of enzymatic C–H functionalization in synthetic design (Figure 3d) [29•]. More recently, they completed the first total synthesis of tambromycin employing a biocatalytic C–H functionalization strategy to access noncanonical amino acid tambroline [30].…”

Section: Biocatalytic Transformations Initiated By Hatmentioning

confidence: 99%

Biocatalytic hydrogen atom transfer: an invigorating approach to free-radical reactions

Nakano

Biegasiewicz

Hyster

2019

Current Opinion in Chemical Biology

View full text Add to dashboard Cite

Initiating and terminating free-radical reactions via hydrogen atom transfer (HAT) is an attractive means of avoiding substrate prefunctionalization. Small molecule catalysts and reagents, however, struggle to execute this fundamental step with useful levels of diastereo- and enantioselectivity. In contrast, nature often carries out HAT with exquisite levels of selectivity for even electronically unactivated carbon–hydrogen bonds. By understanding how enzymes exploit and control this fundamental step, new strategies can be developed to address several long-standing challenges in free-radical reactions. This review will cover recent discoveries in biocatalysis that exploit a HAT mechanism to either initiate or terminate novel one-electron reactions.

show abstract

“…Two additional synthetic steps furnished the targeted MS-153 substrate in 70% overall yield and > 99% ee ( Scheme 15 , Example B) [ 32 ]. Furthermore, a concise synthesis of manzacidin C based on the second generation [ 33 ] chiral silicon Lewis acid, which promoted diastereo- and enantioselective acylhydrazone-alkene [3+2] cycloaddition, has also been reported by the same group [ 34 ]. The corresponding enantioenriched 3,5,5-trisubstituded pyrazolidine precursor was subsequently used for the synthesis of crucial 1,3-bisamide intermediate, which was obtained in 73% yield and high stereoselectivity (>20:1 dr and 94% ee ).…”

Section: Synthesis Of Pyrazolidinesmentioning

confidence: 99%

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

et al. 2017

View full text Add to dashboard Cite

Asymmetric [3+2] cycloadditions of azomethine imines comprise a useful synthetic tool for the construction of pyrazole derivatives with a variable degree of saturation and up to three stereogenic centers. As analogues of pyrrolidines and imidazolidines that are abundant among natural products, pyrazoline and pyrazolidine derivatives represent attractive synthetic targets due to their extensive applications in the chemical and medicinal industries. Following the increased understanding of the mechanistic aspect of metal-catalyzed and organocatalyzed [3+2] cycloadditions of 1,3-dipoles gained over recent years, significant strides have been taken to design and develop new protocols that proceed efficiently under mild synthetic conditions and duly benefit from superior functional group tolerance and selectivity. In this review, we represent the current state of the art in this field and detailed methods for the synthesis of non-racemic pyrazolines and pyrazolidines via [3+2] metal and organocatalyzed transformations reported since the seminal work of Kobayashi et al. and Fu et al. in 2002 and 2003 up to the end of year 2017.

show abstract

An Efficient Asymmetric Synthesis of Manzacidin C

Cited by 57 publications

References 16 publications

Synthetic approaches towards alkaloids bearing α-tertiary amines

Synthetic approaches towards alkaloids bearing α-tertiary amines

Biocatalytic hydrogen atom transfer: an invigorating approach to free-radical reactions

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

Contact Info

Product

Resources

About