Mechanistic dichotomy in the solvent dependent access to <i>E vs. Z</i>-allylic amines <i>via</i> decarboxylative vinylation of amino acids

Manna, Samir; Kakumachi, Shunta; Das, Kanak Kanti; Tsuchiya, Youichi; Adachi, Chihaya; Panda, Santanu

doi:10.1039/d2sc02090d

Cited by 22 publications

(25 citation statements)

References 61 publications

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“…Vinyl bromides containing synthetically versatile functional groups, such as silane ( 16 ), ester ( 17 and 25 ), chloride ( 18 and 19 ), alcohol ( 20 ), and pyridine ( 26 ) were all compatible with the reaction conditions. In cases of styrenyl derivatives, a slight decrease in the E :Z ratio was observed ( 23 and 24 ) …”

Section: Results and Discussionmentioning

confidence: 99%

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Lu,

Yao,

et al. 2023

J. Am. Chem. Soc.

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Section: Results and Discussionmentioning

confidence: 99%

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Lu,

Yao,

et al. 2023

J. Am. Chem. Soc.

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“…Earlier in 2014, the MacMillan group reported a Ir‐complex ( P2 ) catalyzed allylation with a as high as 98 : 2 ( Z/E ) selectivity ( 76 a ), but unfortunately, the E ‐isomer could not be obtained purely due to the limited available energy‐gap between the photocatalyst and product (Scheme 24 condition A) [40] . Very recently, the Panda group elegantly realized Z ‐ and E ‐isomer selectivity in an excellent fashion by carefully tuning the reaction conditions (Scheme 24, condition B/C) [41] . Interestingly, slightly change of solvents and reaction temperatures, trans / cis ‐isomers 76 can be selectively generated.…”

Section: Neas As α‐Amino Alkyl Sourcementioning

confidence: 99%

α‐Amino Acids: An Emerging Versatile Synthon in Visible Light‐Driven Decarboxylative Transformations

Shao

Ban

2023

The Chemical Record

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Abstractα‐Amino acids have been widely recognized as environmental‐benign and non‐fossil carbon sources both in biological and synthetic chemistry. In recent years, with the remarkable development of visible‐light photocatalysis in organic synthesis, α‐amino acid and its derivatives have received tremendous attention as radical precursors via photocatalyzed decarboxylation, thus realizing diverse aminoalkylated transformations or constructions of novel N‐bearing heterocyclic motifs by taking advantage of N‐atoms from α‐amino acid. This review aims to provide a comprehensive update on the recent exploitation of α‐amino acids in visible light photocatalysis, with particular emphasis on the types of α‐amino acids employed and their distinct mechanisms applied wherein.

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“…Despite several developments in this area, no single method is ideal for achieving optimal stereoselectivity for diverse olefins due to their electronic and steric differences. The development of a uniform strategy to access both E ‐ and Z ‐isomer of a different class of olefins is limited [2a–c] . Standard olefination methods like Wittig, HWE protocol, Julia olefinations suffer from poor regioselectivity due to steric effect in the transition state [2d–e] .…”

Section: Introductionmentioning

confidence: 99%

Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy

et al. 2023

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Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π‐systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3‐dienes in good yield and up to 100% stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z‐vinyl heteroarenes for different heteroarenes under identical conditions. Density functional theory (DFT) investigations unveil the mechanistic dichotomy between olefin and heteroarene activation followed by 1,2‐migration, leading to E or Z‐vinyl heteroarenes respectively. We also report a previously unknown reversal of stereoselectivity by using 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an electrophile. The Zweifel olefination using a boronate complex that carries two different olefins was previously unexplored due to significant challenges associated with the site‐selective activation of olefins. We have solved this problem and reported the site‐selective activation of olefins for the stereoselective synthesis of 1,3‐dienes.

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Mechanistic dichotomy in the solvent dependent access to E vs. Z-allylic amines via decarboxylative vinylation of amino acids

Abstract: Solvent plays an important role in the photophysical property of donor-acceptor-based photocatalysts. The solvent-dependent access to E vs Z-allylic amines was achieved via decarboxylative vinylation of amino acids with vinyl...

Cited by 22 publications

References 61 publications

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

α‐Amino Acids: An Emerging Versatile Synthon in Visible Light‐Driven Decarboxylative Transformations

Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy

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