Practical regio- and stereoselective azidation and amination of terminal alkenes

Ojo, Olatunji S.; Miranda, Octavio; Baumgardner, Kyle C.; Bugarin, Alejandro

doi:10.1039/c8ob02734j

Cited by 11 publications

(19 citation statements)

References 39 publications

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“…The following cinnamyl azides were prepared through known procedures and have been previously characterized: 1a , , 1c – 1d , , 1e – 1f , , 1g , , 1h , , 1j – 1k , , 1o , , 1p – 1q , 1t , ,, 1u – 1v , 1w , − and 1hh . , …”

Section: Methodsmentioning

confidence: 99%

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A Cascade Reaction of Cinnamyl Azides with Acrylates Directly Generates Tetrahydro-Pyrrolo-Pyrazole Heterocycles

2020

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Developing reactions to generate complex and modular building blocks in a concise and direct fashion remains a contemporary synthetic challenge. This work describes a stereoselective cascade reaction between allylic azides and acrylates that directly generates tetrahydro-pyrrolo-pyrazole ring systems. These products contain up to four contiguous stereocenters, two of which may be tetrasubstituted carbon atoms attached to a nitrogen atom.Over 30 examples are provided with an average isolated yield of 71% (ranging from 40% to 94%). The reaction was easily scaled to use more than one gram of starting material, and the products can be readily diversified.

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Section: Methodsmentioning

confidence: 99%

“…Azide Synthesis. The following cinnamyl azides were prepared through known procedures and have been previously characterized: 1a, 44,45 1c−1d, 44,45 1e−1f, 44,46 1g, 44,47 1h, 18,44 1j−1k, 44,47 1o, 44,45 1p−1q, 44 1t, 46,48,49 1u−1v, 30 1w, 49−51 and 1hh. 18,44 2-Nitrocinnamylazide (1b).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

A Cascade Reaction of Cinnamyl Azides with Acrylates Directly Generates Tetrahydro-Pyrrolo-Pyrazole Heterocycles

2020

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“…For example, in a typical experiment using an H-Cube ® , ( S )- 7 gave the saturated N -Boc-protected sulfone ( S )- 8 in reasonably good yield (Scheme 2 ). Alternative methods reported for the conversion of azides into amides and carbamates, including, for example, traceless Staudinger reactions 11 and hydrogenolysis with Lindlar’s catalyst, 12 proved not to be feasible for the synthesis of 3 .…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

Evans¹,

Shen²,

Cunningham³

2022

Synthesis

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The enantioselective azo-based α-amination of an aldehyde followed by a Horner–Wadsworth–Emmons-based vinyl sulfone formation is reported. The thus obtained optically active N,N′-diprotected trans-(phenylsulfonyl)vinyl hydrazine products were then converted into the corresponding N-functionalised trans-(phenylsulfonyl)vinyl amines. Specifically, reaction of 4-phenylbutanal with di-tert-butyl azodicarboxylate (DBAD) in the presence of l- or d-proline, followed by addition of diethyl [(phenylsulfonyl)methyl]phosphonate, gave either enantiomer of di-tert-butyl trans-1-[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]hydrazine-1,2-dicarboxylate. The enantiomeric excesses of the (+)- and (–)-enantiomers prepared in this manner were in the range 86–89%. The conversion of these γ-hydrazino vinyl sulfones into the corresponding γ-amino-substituted compounds was achieved following a Boc deprotection, Zn reduction, N-functionalisation sequence. This three-step sequence was reasonably efficient (approx. 50%) and no erosion of enantiopurity was found to have taken place. The compounds accessed via this process include both enantiomers of tert-butyl trans-[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]carbamate and epimeric dipeptide mimetics including 4-methyl-N-{(S)-1-oxo-3-phenyl-1-[((S,E)-5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl)amino]propan-2-yl}piperazine-1-carboxamide (also known as K777).

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“…The yields for the KO t Bu-mediated transformation are presented below in Tables –, whereas the yields using DBU are shown in the Supporting Information (Tables SI, 1–3). This study was performed to compare the result from our recently reported regio-and stereoselective nucleophilic addition to miscellaneous terminal olefins. , In our prior work, DBU was the best base to afford allylic adducts from electron-poor or weak electron-donating substrates. However, for this work, KO t Bu was deemed superior base for the observed rearrangement of electron-rich substrates (i.e., estragole and safrole).…”

Section: Resultsmentioning

confidence: 99%

One-Pot Synthesis of α-Alkyl Styrene Derivatives

Ojo

Bugarin

2021

ACS Omega

Self Cite

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There is a significant need to develop more rapid and efficient routes to styrene derivatives, since they are extensively used in polymer sciences. This manuscript reports a one-pot synthesis of an array of α-alkyl styrene derivatives from readily available natural products (i.e., estragole and safrole). This method is regioselective, producing a rearranged adduct, under transition metal-free conditions. This methodology has broad nucleophile scope, even tolerating sterically hindered nucleophiles; it is general for carbon, nitrogen, oxygen, and sulfur nucleophiles.

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Practical regio- and stereoselective azidation and amination of terminal alkenes

Abstract: A metal-free synthesis of allylic azides and allylic amines was achieved under mild reaction conditions, which represents a milder alternative for azidation and amination reactions.

Cited by 11 publications

References 39 publications

A Cascade Reaction of Cinnamyl Azides with Acrylates Directly Generates Tetrahydro-Pyrrolo-Pyrazole Heterocycles

A Cascade Reaction of Cinnamyl Azides with Acrylates Directly Generates Tetrahydro-Pyrrolo-Pyrazole Heterocycles

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

One-Pot Synthesis of α-Alkyl Styrene Derivatives

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