Facile Conversion of Primary and Secondary Alcohols to Alkyl Iodides

Lange, Gordon L.; Gottardo, Christine

doi:10.1080/00397919008052864

Cited by 134 publications

(67 citation statements)

References 11 publications

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“…These were synthesized by first converting PFPP-OH to 1-iodo-3-pentafluorophenyl propane. This reaction was carried out in DCM with argon at room temperature according to the method of Lange and Gottardo (27). Triphenyl phosphine (Aldrich) was dissolved followed by the addition of imidazole (Aldrich), and the ingredients were allowed to mix for 30 min prior to the addition of iodine.…”

Section: ])mentioning

confidence: 99%

Use of a Novel Fluorinated Organosulfur Compound To Isolate Bacteria Capable of Carbon-Sulfur Bond Cleavage

Hamme

Fedorak

Foght

et al. 2004

Appl Environ Microbiol

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The vacuum residue fraction of heavy crudes contributes to the viscosity of these oils. Specific microbial cleavage of COS bonds in alkylsulfide bridges that form linkages in this fraction may result in dramatic viscosity reduction. To date, no bacterial strains have been shown conclusively to cleave COS bonds within alkyl chains. Screening for microbes that can perform this activity was greatly facilitated by the use of a newly synthesized compound, bis-(3-pentafluorophenylpropyl)-sulfide (PFPS), as a novel sulfur source. The terminal pentafluorinated aromatic rings of PFPS preclude growth of aromatic ring-degrading bacteria but allow for selective enrichment of strains capable of cleaving COS bonds. A unique bacterial strain, Rhodococcus sp. strain JVH1, that used PFPS as a sole sulfur source was isolated from an oil-contaminated environment. Gas chromatography-mass spectrometry analysis revealed that JVH1 oxidized PFPS to a sulfoxide and then a sulfone prior to cleaving the COS bond to form an alcohol and, presumably, a sulfinate from which sulfur could be extracted for growth. Four known dibenzothiophene-desulfurizing strains, including Rhodococcus sp. strain IGTS8, were all unable to cleave the COS bond in PFPS but could oxidize PFPS to the sulfone via the sulfoxide. Conversely, JVH1 was unable to oxidize dibenzothiophene but was able to use a variety of alkyl sulfides, in addition to PFPS, as sole sulfur sources. Overall, PFPS is an excellent tool for isolating bacteria capable of cleaving subterminal COS bonds within alkyl chains. The type of desulfurization displayed by JVH1 differs significantly from previously described reaction results.Microbial methods of removing sulfur from organosulfur compounds are of interest to the petroleum industry for reducing sulfur emissions and, more recently, for reducing heavy oil viscosity. As conventional crude oils are consumed throughout the world, heavier oils are being exploited which, due to their high viscosity, cannot be transported from remote field sites to refineries without adding diluents. The vacuum residue fraction of crude oils (boiling point Ն 524°C [975°F]) contributes to viscosity, and recent models indicate that alkyl sulfides compose important bridges in the network of high-molecularweight molecules in this fraction (34). Up to 40% of the sulfur in these fractions is in the form of alkyl sulfides; if these alkyl COS bonds can be selectively cleaved using a biological catalyst, reductions in molecular size and viscosity could occur.The first requirement for developing a biological process for heavy oil viscosity reduction is obtaining a microorganism capable of alkyl COS bond cleavage without reducing the carbon value of the substrate. Precedence for this type of reaction with aromatic heterocycles can be found in the well-characterized 4S pathway that selectively removes sulfur from dibenzothiophene (DBT) (35). The dsz or sox operon (genes responsible for DBT desulfurization) (7,38) in Rhodococcus sp. strain IGTS8 has been observed in a variety of ...

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Section: ])mentioning

confidence: 99%

Use of a Novel Fluorinated Organosulfur Compound To Isolate Bacteria Capable of Carbon-Sulfur Bond Cleavage

Hamme

Fedorak

Foght

et al. 2004

Appl Environ Microbiol

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“…These 1,10-phenanthrolines 3 and 4 were used as ligands for copper(I), and the resulting complexes were tested in the cyclopropanation of indene (28) with ethyl diazoacetate (26). Unfortunately, the influences of the ligands on the exo/endo stereoselectivities were small but the ring size dependence indicates that higher selectivities might be expected for macrocycles with smaller ring sizes.…”

Section: Discussionmentioning

confidence: 99%

“…In addition to cyclopropanes, diethyl fumarate (30) and maleate (31) are usually detected as by-products ( Figure 9). (28) with ethyl diazoacetate (26). In addition to the cyclopropanes exo-29 and endo-29, diethyl fumarate (30) and diethyl maleate (31) are always found as by-products.…”

Section: 10-phenanthroline-based Ligands In Cyclopropanationsmentioning

confidence: 99%

“…Table 5. Results of the copper(I)-catalysed cyclopropanations of indene (28) with ethyl diazoacetate (26) in the presence of a range of 1,10-phenanthrolines 3 and 4. For comparison with previous results, the yields and selectivities obtained with the phenanthrolinebridged calix [6]arene 2a and the bimacrocyclic phenanthroline 1b with bis-ortho-substituted bridgeheads with chain lengths of 10 carbon atoms are shown (n.m.: not measured).…”

Section: 10-phenanthroline-based Ligands In Cyclopropanationsmentioning

confidence: 99%

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Concave 1,10‐Phenanthrolines as Ligands for Cyclopropanations – Towards a Deeper Understanding of the Stereoselectivity

Eggers

Lüning

2009

Eur J Org Chem

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“…Já o uso de PPh 3 /imidazol/I 2 em CH 2 Cl 2 à t.a. 35 promoveu a formação do iodo diazo éster esperado 24, porém na forma de uma mistura 2:1 com o produto de desidroalogenação 8. Não foi possível separar os compostos 8 e 24 por cromatografia, e desse modo a mistura 24/8 (2:1) foi tratada com Rh 2 (OAc) 4 à t.a.. Mais uma vez, entretanto, não se obtiveram resultados favoráveis, observando-se apenas a formação de uma mistura complexa de produtos, a partir do consumo total de 24 (e parcial de 8).…”

Section: Esquema 10unclassified

Reações de inserção intramolecular de diazo compostos polifuncionais catalisadas por ródio(II): síntese de oxetan-3-ona-2-carboxilato e outros heterociclos funcionalizados

Padwa¹,

Sá²

1999

Quím. Nova

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Recebido em 4/1/99; aceito em 31/3/99 RHODIUM(II)-CATALYSED INTRAMOLECULAR INSERTION REACTION OF MULTIFUNC-TIONAL DIAZO COMPOUNDS: SYNTHESIS OF OXETAN-3-ONE-2-CARBOXILATE AND OTHER HETEROCYCLES.γ-Hydroxy-α-diazo-β-ketoesters are key intermediates in the chemistry of penicilin-based antibiotics and natural products. The method developed here for the synthesis of ethyl 2-diazo-4-hydroxy-3-oxo-butanoate 17 (in two steps from the diazo mercurial 2) compares very favorably with those reported in the literature for similar compounds. The Rh 2 (OAc) 4 -mediated intramolecular OH-insertion reaction of the diazo hydroxy ester 17 was investigated, furnishing the oxetan-3-one-2-carboxilate 18 in good yield. When the diazo ester lacks a free hydroxyl group as in the case of the phenoxy diazo ester 11 an intramolecular CH-insertion takes place, affording the 2H-chromene 20 in almost quantitative yield. The behavior of other functionalized diazo esters towards Rh 2 (OAc) 4 was also investigated.Keywords: diazoesters; intramolecular insertion reaction; rhodium carbenoid. ARTIGO INTRODUÇÃOA utilização de compostos α-diazo carbonilados em síntese orgânica tem se apresentado como um excelente método na preparação de sistemas estruturalmente complexos, como heterociclos e produtos naturais. A razão para isso reside no fato de que compostos α-diazo carbonilados participam em uma grande variedade de transformações químicas, incluindo ciclopropanação, rearranjo de Wolff, dimerização, α,α-substituição, X-H inserção (X= C, O, N, S), cicloadição, formação de ilídeos, etc. Todos esses processos podem ocorrer tanto inter como intramolecularmente, através da eliminação de nitrogê-nio molecular [1][2][3][4][5][6][7] . A recente descoberta de que metais de transição (especialmente ródio(II)) catalisam a eliminação de N 2 em compostos α-diazo carbonilados promovendo a formação de metalocarbenóides como intermediários reativos fez aumentar ainda mais o interesse em sistemas contendo um grupo diazo (Figura 1) [1][2][3][4][5] . A exploração sintética destes fenômenos (particularmente em reações de ciclopropanação, inserção e cicloadições) está intimamente associada aos estudos mecanísticos envolvendo o comportamento dos metais de transição no processo catalítico e na geração das espécies reativas. Uma grande variedade de heterociclos é obtida a partir de reações de inserção de diazo compostos catalisada por ródio(II) (Equação 1). Já a presença de um grupo carbonilado δ Endereço atual para correspondência: Departamento de Química, Universidade Federal de Santa Catarina, Campus de Trindade, 88040-900, Florianópolis, SC e-mail: msa@qmc.ufsc.br adequadamente distante da função diazo permite a formação de ilídeos reativos, participantes em reações de cicloadição 1,3 dipolar gerando oxabiciclos (Equação 2) 1-5 . Figura 1O desenvolvimento de metodologias eficientes na preparação de compostos α-diazo carbonilados tem permitido o acesso cada vez maior a estes sistemas [5][6][7][8][9] . Um método para a construção de compostos α-diazo carbonilados que tem...

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Facile Conversion of Primary and Secondary Alcohols to Alkyl Iodides

Cited by 134 publications

References 11 publications

Use of a Novel Fluorinated Organosulfur Compound To Isolate Bacteria Capable of Carbon-Sulfur Bond Cleavage

Use of a Novel Fluorinated Organosulfur Compound To Isolate Bacteria Capable of Carbon-Sulfur Bond Cleavage

Concave 1,10‐Phenanthrolines as Ligands for Cyclopropanations – Towards a Deeper Understanding of the Stereoselectivity

Reações de inserção intramolecular de diazo compostos polifuncionais catalisadas por ródio(II): síntese de oxetan-3-ona-2-carboxilato e outros heterociclos funcionalizados

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