Quinones Having Vitamin K Activity

Fieser, Louis; Bowen, Douglas M.; Campbell, William P.; Fieser, Mary; Fry, Edward M.; Jones, Richard N.; Riegel, Byron; Schweitzer, Carl E.; Smith, Perrin G.

doi:10.1021/ja01876a507

Cited by 33 publications

(9 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We propose that the formation of 14 in the iron-porphyrinate-catalyzed oxidations arises oia acid-catalyzed rearrangement of the initially formed epoxide 15 . This represents the shortest and highest-yielding preparation of 14 [37]. The same reaction in pure CH,Cl, yielded 40% of 14 (turnover number = 7), a much higher yield than had been previously reported [ 16~1.…”

Section: ' H -N M R Binding Studies Withsupporting

confidence: 49%

“…30 min, the mixture did not show any more changes since the porphyrin catalyst was completely bleached. The more polar product was isolated and identified by 'H-NMR, MS, and IR as acenaphthen-1-one [37] (14; Scheme 3). The initially formed less polar compound was identified as epoxide 15, which was independently prepared by oxidation of acenaphthylene with 3-chloroperbenzoic acid [38].…”

Section: ' H -N M R Binding Studies Withmentioning

confidence: 99%

See 1 more Smart Citation

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Benson

Valentekovich

Tam

et al. 1993

Helvetica Chimica Acta

View full text Add to dashboard Cite

Following a known synthetic procedure, the porphyrin‐cyclophane 1 having a porphyrin attached by two straps to an apolar cyclophane binding site was prepared. Upon metallation, the ZnII and FeIII derivatives 2 and 3, respectively, were obtained in good yields. Treatment of 3 with base yielded the μ‐oxo dimer 4 in which the two oxo‐bridged porphyrins moieties are both capped by cyclophane binding sites. All compounds 1–4 are freely soluble in protic solvents such as MeOH and CF3CH2OH, and the FeIII derivatives 3 and 4 are active cytochrome P‐450 mimics in these protic environments. Strong inclusion complexation of polycyclic aromatic hydrocarbons by 1 and 3 in alcoholic solvents was observed and quantified by 1H‐NMR and UV/VIS titrations. Acenaphthylene binds in an ‘equatorial’ orientation which locates its reactive 1,2‐double bond near the porphyrin center, whereas phenanthrene binds ‘axially’ with the reactive 9,10‐double bond oriented away from the porphyrin. The reduction potential of 3 was not significantly altered by substrate binding. In the unbound form, the FeIII center in porphyrin 3 was found by ESR and 1H‐NMR to prefer a high‐spin state (S = 5.2). In CF3CH2OH, using iodosylbenzene as O‐transfer agent, the FeIII derivative 3 catalyzed the oxidation of acenaphthylene to acenaphthen‐1‐one (14). Phenanthrene inhibited the reaction, possibly as a result of strong but nonproductive binding. Under similar conditions, isotetralin (18) was aromatized with high turnover to 1,4‐dihydronaphthalene. The μ‐oxo dimer 4 also showed high activity in the oxidation of acenaphthylen in MeOH, a result which provides strong evidence for efficent supramolecular catalysis. Due to as yet unknown reaction channels leading to polymeric products, poor mass balances were generally obtained in the oxidations effected in MeOH and CF3CH2OH in the presence of PhIO.

show abstract

Section: ' H -N M R Binding Studies Withsupporting

confidence: 49%

Section: ' H -N M R Binding Studies Withmentioning

confidence: 99%

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Benson

Valentekovich

Tam

et al. 1993

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Fieser summarized the saga in a lecture on October 24, 1939, that was published in January 1940,12i and noted his group began work on May 18, 1939, inspired by the work already published by others and his long experience in quinone chemistry. His first paper on the subject was submitted on June 12, 1939 12a. Fieser begins his report “I have a story to tell tonight about the naming of a cat” and describes how their latest Siamese cat was born that year, and named in honor of vitamin K 12j…”

Section: Vitamin K and The Race For The Nobel Prizementioning

confidence: 99%

Louis Fieser: An Organic Chemist in Peace and War

Lenoir

Tidwell

2009

Eur J Org Chem

View full text Add to dashboard Cite

Louis Frederick Fieser (1899–1977) was an prominent figure among organic chemists of the mid‐20th century, identified today for Reagents for Organic Synthesis, co‐authored with his wife Mary Fieser, and now available electronically. Fieser was first known for his prolific research efforts in quinones, polycyclic aromatics, and steroids, and was also a leading educator and public servant. His activities included not only major achievements in cancer research and cancer prevention through the suppression of smoking, but also participation in war research and the invention of napalm, which are part of his legacy.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

show abstract

“…The foregoing observations stimulated considerable activity directed toward isolation of natural vitamin K. In the period 1935-1939, various workers (Almquist and Stokstad, 4 Almquist,5,6 Dam, 34 Dam and colleagues,a5 Thayer, Doisy, and associates/O! and McKee, Doisy, and co-workers 69 ) reported the isolation of vitamin K from alfalfa leaf meal (vitamin K 1 ) or putrefied fish meal (vitamin K2)' Further research led to the determination of the chemical structure of the naturally occurring K vitamins, synthesis of vitamin Kl> and synthesis of numerous quinone compounds with varying degrees of vitamin K activity (Fieser,43 Fieser and associates, 44 Binkley, Doisy, and colleagues/ 8 ,19 Almquist and Klose, 7 and Ansbacher and Fernholz 10 ). Vitamin K1 (phytonadione; 2-methyl-3phytyl-1,4-naphthoquinone) is the only naturally occurring K vitamin available for clinical use.…”

Section: Isolation and Chemistrymentioning

confidence: 99%

Vitamin K₁ and the vitamin K analogues

Finkel

1961

Clin Pharma and Therapeutics

View full text Add to dashboard Cite

The use of vitamin Kl and various preparations with vitamin K activity in the treatment of hypoprothrombinemic states has long been a well-established procedure. Because the K analogues have often been popularly referred to as vitamin K, confusion has arisen regarding the relationship between these compounds and the true vitamin K. Two types of vitamin K have been found in Nature: vitamin K1, present in various green vegetables, cereals, seeds, tomatoes, and liver, and vitamin K" isolated from putrefied fish meal. The former has been synthesized and represents the commercially available form of the true vitamin. The K analogues were originally synthesized in an attempt to find compounds with more potent antihemorrhagic activity or substances which could be administered more easily than the early preparations of vitamin K1• This article reviews pertinent aspects of the voluminous literature on vitamin Kl and the K analogues and presents the recorded differences (or similarities) in effectiveness and toxicity between the two types of compounds in various clinical states.

show abstract

Quinones Having Vitamin K Activity

Cited by 33 publications

References 0 publications

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Louis Fieser: An Organic Chemist in Peace and War

Vitamin K₁ and the vitamin K analogues

Contact Info

Product

Resources

About

Quinones Having Vitamin K Activity

Cited by 33 publications

References 0 publications

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Catalytic Cyclophanes. Part VIII. Cytochrome P‐450 activity of a porphyrin‐bridged cyclophane

Louis Fieser: An Organic Chemist in Peace and War

Vitamin K1 and the vitamin K analogues

Contact Info

Product

Resources

About

Vitamin K₁ and the vitamin K analogues