Pyridinium oxidations of benzyl alcohol under microwave-assisted retro-ene conditions

Jensen, Anton W.; Moore, John M.; Kimble, Mary Ellen V.; Ausmus, Alex P.; Dilling, Wendell L.

doi:10.1016/j.tetlet.2016.11.013

Cited by 3 publications

(1 citation statement)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Until recently, it was thought that these reactions occurred via a hydride-transfer mechanism, in which a hydride is trans- ISSN 2053ISSN -2296 # 2017 International Union of Crystallography ferred from (3) to a hydride acceptor, forming (2) (Abeles et al, 1957). However, recent studies on NAD(P)H enzymes and models have revealed that they most likely operate through an ene/retro-ene reaction (Rosenthal et al, 2014;Libby & Mehl, 2012;Jensen et al, 2016), for example, with lactate dehydrogenase, LDH, as shown in Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH

et al. 2017

Self Cite

View full text Add to dashboard Cite

3-Aminocarbonyl-1-benzylpyridinium bromide (N-benzylnicotinamide, BNA), CHNO·Br, (I), and 1-benzyl-1,4-dihydropyridine-3-carboxamide (N-benzyl-1,4-dihydronicotinamide, rBNA), CHNO, (II), are valuable model compounds used to study the enzymatic cofactors NAD(P) and NAD(P)H. BNA was crystallized successfully and its structure determined for the first time, while a low-temperature high-resolution structure of rBNA was obtained. Together, these structures provide the most detailed view of the reactive portions of NAD(P) and NAD(P)H. The amide group in BNA is rotated 8.4 (4)° out of the plane of the pyridine ring, while the two rings display a dihedral angle of 70.48 (17)°. In the rBNA structure, the dihydropyridine ring is essentially planar, indicating significant delocalization of the formal double bonds, and the amide group is coplanar with the ring [dihedral angle = 4.35 (9)°]. This rBNA conformation may lower the transition-state energy of an ene reaction between a substrate double bond and the dihydropyridine ring. The transition state would involve one atom of the double bond binding to the carbon ortho to both the ring N atom and the amide substituent of the dihydropyridine ring, while the other end of the double bond accepts an H atom from the methylene group para to the N atom.

show abstract

Section: Introductionmentioning

confidence: 99%

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

The growing relevance of biological ene reactions

Jensen

Mohanty

Dilling

2019

Bioorganic & Medicinal Chemistry

View full text Add to dashboard Cite

A Comparison between KBH4 and NaBH4 in Their Reduction of Pyridinium Salts

Luo¹,

Hao²,

Zhu³

et al. 2019

HETEROCYCLES

View full text Add to dashboard Cite

Pyridinium oxidations of benzyl alcohol under microwave-assisted retro-ene conditions

Cited by 3 publications

References 26 publications

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH

The growing relevance of biological ene reactions

A Comparison between KBH4 and NaBH4 in Their Reduction of Pyridinium Salts

Contact Info

Product

Resources

About

Pyridinium oxidations of benzyl alcohol under microwave-assisted retro-ene conditions

Cited by 3 publications

References 26 publications

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD+ and NADH

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD+ and NADH

The growing relevance of biological ene reactions

A Comparison between KBH4 and NaBH4 in Their Reduction of Pyridinium Salts

Contact Info

Product

Resources

About

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH

N-Benzylnicotinamide and N-benzyl-1,4-dihydronicotinamide: useful models for NAD⁺ and NADH