On the mechanism of hydrogen transfer by nicotinamide coenzymes and some dehydrogenases

Laurie, David J.; Lucas, Edward; Nonhebel, D. C.; Suckling, Colin J.; Walton, John C.

doi:10.1016/s0040-4020(01)87508-6

Cited by 25 publications

(9 citation statements)

References 51 publications

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“…Potassium Cyclopropylglyoxylate (6) [23] To a mechanically stirred mixture of cyclopropyl methyl ketone (5) (54.6 g, 0.65 mol) and a solution of Na 2 CO 3 (0.8 g, 7.6 mmol) in water (360 mL) at 50 8C in a 4 L flask equipped with an efficient reflux condenser and a 500 mL dropping funnel, was added dropwise over 40 h a solution of KMnO 4 (145 g, 0.92 mol) in water (3 L). The mixture was stirred for an additional 10 h, then cooled to room temperature, and MeOH (360 mL) was added.…”

Section: Methodsmentioning

confidence: 99%

Practical Syntheses of Both Enantiomers of Cyclopropylglycine and of Methyl 2‐Cyclopropyl‐2‐N‐Boc‐iminoacetate

Larionov

Meijere

2006

Adv Synth Catal

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: A facile three-step synthesis of racemic cyclopropylglycine in multigram quantities from inexpensive cyclopropyl methyl ketone has been elaborated. Enzymatic hydrolysis of the N-Boc-protected methyl ester of cyclopropylglycine 9 with the inexpensive enzyme papain from Carica papaya affords both enantiomers of cyclopropylglycine (8) with enantiomeric excesses of 99 % or better after deprotection under acidic conditions. Furthermore, the new cyclopropyl group-containing building block methyl 2-cyclopropyl-2-N-Boc-iminoacetate (13) was prepared by N-chlorination and subsequent dehydrochlorination with 1,8-diazabicycloA C H T U N G T R E N N U N G [5.4.0]undec-7-ene (DBU). Addition of nucleophiles to 13 offers a ready access to an unusual, orthogonally bisprotected a,a-diamino acid derivative and interesting components of rigid peptide backbones.

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Section: Methodsmentioning

confidence: 99%

Practical Syntheses of Both Enantiomers of Cyclopropylglycine and of Methyl 2‐Cyclopropyl‐2‐N‐Boc‐iminoacetate

Larionov

Meijere

2006

Adv Synth Catal

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“…Pentane, hexane, 1,3-cyclohexadiene, tert-butyl methyl ether, oxalyl chloride, methyl and ethyl chlorooxalate, lithium hydroxide monohydrate, sodium cyanide, activated manganese() oxide, 10 wt.-% Pd/C, dirhodium tetraacetate, methyltriphenylphosphonium bromide, potassium tert-butoxide, n-butyllithium solution in hexane, 2,6-ditert-butyl-4-methylphenol (BHT), dimethyl trans-cyclopropane-1,2-dicarboxylate (3d) and aliphatic urethane dimethacrylate (UDMA, Ivoclar Vivadent, from 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylenediisocyanate) were used as supplied without further purification. 1,1-Bis(ethoxycarbonyl)-2-vinylcyclopropane [17] (DECVCP), methylenecyclopropane [18] (2b), bicyclopro-pylidene [19] (2c), dimethyl bicyclo[3.1.0]hexane-6,6-dicarboxylate [20] (3f), diethyl 2-formylcyclopropane-1,1-dicarboxylate [7] (5e), potassium cyclopropyloxoacetate, [21] methyl and ethyl diazopyruvate, [22] 3,3-dimethylcyclobutyl bromide, [23] ethyl trans-(2-ethenylcyclopropyl)oxoacetate (7g) and ethyl trans-2-(2-ethenylcyclopropyl)-propenoate [13] (1g) were prepared as described previously. 2,2Ј-Azobisisobutyronitrile (AIBN) was purified by recrystallization from methanol.…”

Section: Radical Polymerizations Of 2-cyclopropylacrylates 1a؊nmentioning

confidence: 99%

Synthesis and Radical Polymerization of Various 2‐Cyclopropylacrylates

Meijere¹,

Bagutski²,

Zeuner³

et al. 2004

Eur J Org Chem

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Fourteen new alkyl 2-cyclopropylacrylates 1a−n with various substituents R 1 −R 5 were synthesized from readily available precursors by applying standard transformations such as cyanohydrin formation from an aldehyde, alcoholysis to an α-hydroxycarboxylic ester, oxidation and Wittig methylenation of an α-oxocarboxylic ester. Overall yields ranged from 33 to 54%. A new method for the hydrolysis of dimethyl cyclopropanedicarboxylates to the corresponding half-esters was developed. The α-oxocarboxylates 7g−n were prepared by dirhodium tetraacetate catalyzed cyclopropanation of alkenes 8g−n with methyl or ethyl diazopyruvate in 32−58% yield. The monomers 1a−n were characterized by 1 H, 13 C NMR spectroscopy, mass spectrometry and elemental analysis. The radical homopolymerizations of 1a−n were carried out with 2,2Ј-azabisisobutyronitrile (AIBN) as initiator in chloroben-

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“…Thus the introduction of a single oxygen substituent caused a decrease in the rate of ring opening by only a factor of 10 and hence for alcohol dehydrogenase, the mechanistic probe passed this test. [44,45. ''I1 In contrast, the rate of ring opening of cyclopropylalkyl radicals doubly substituted with a donor and an acceptor group was not measurable by ESR spectroscopy under accessible conditions.…”

Section: The Mechanism Of Hydrogen Transfer By Nicotinamide Coenzymesmentioning

confidence: 99%

“…This result could be accounted for by an addition mechanism (see Section 4), but when it was found that N-benzyl-1-methylcyclopropylamine 43 was also an irreversible inhibitor, the possibility of an alternative mechanism became strong, because this inhibitor clearly cannot form a cyclopropanone equivalent. The radical cation 44 was implicated and two modes of reaction were postulated (Fig. 7); firstly, the ring-opening reaction of a cyclopropylalkyl radical equivalent leading to 45; secondly, ring expansion to an azetidinium radical cation 46.…”

mentioning

confidence: 99%