scholarly journals Selective Terminal Functionalization of Linear Alkanes

2021 ◽  
Author(s):  
Ilan Marek ◽  
Jeffrey Bruffaerts ◽  
Keren Buhnik-Rosenblau ◽  
Anthony Cohen ◽  
Inbar Kesten ◽  
...  
Keyword(s):  
Mutant Strain ◽  
Large Array ◽  
Linear Alkanes ◽  
Metal Catalyzed ◽  
Sequential Strategy

Abstract Selective undirected functionalization of strong primary C-H bonds of linear alkanes, that do not possess directing groups, historically stands as one of the most challenging transformation in chemistry. In this Article, we report a two-step sequential strategy involving a biocatalytic dehydrogenation / remote hydrofunctionalization, as a unified and versatile approach to selectively convert linear alkanes into a large array of valuable functionalized aliphatic derivatives. The dehydrogenation is carried out by a mutant strain of Rhodococcus and the produced alkenes are subsequently engaged in a remote functionalization through a metal-catalyzed hydrometalation/migration sequence that subsequently react with a large variety of electrophiles. The judicious implementation of this combined biocatalytic and organometallic approach enabled us to develop a high-yielding protocol to site-selectively functionalize unreactive primary C–H bonds.

scholarly journals Parvibaculum lavamentivorans DS-1T Degrades Centrally Substituted Congeners of Commercial Linear Alkylbenzenesulfonate to Sulfophenyl Carboxylates and Sulfophenyl Dicarboxylates

2007 ◽  
Vol 73 (15) ◽  
pp. 4725-4732 ◽  
Author(s):  
David Schleheck ◽  
Thomas P. Knepper ◽  
Peter Eichhorn ◽  
Alasdair M. Cook
Keyword(s):  
Mass Spectrometry ◽  
High Pressure ◽  
Liquid Chromatography ◽  
Electrospray Ionization ◽  
Electrospray Ionization Mass Spectrometry ◽  
Ion Trap ◽  
Ionization Mass ◽  
Large Array ◽  
Linear Alkylbenzenesulfonate ◽  
Linear Alkanes

ABSTRACT Commercial linear alkylbenzenesulfonate (LAS) contains 20 congeners of linear alkanes (C10 to C13) substituted subterminally with the 4-sulfophenyl moiety in any position from lateral to central. Parvibaculum lavamentivorans DS-1T degrades each of eight laterally substituted congeners [e.g., 2-(4-sulfophenyl)decane (2-C10-LAS); herein, compounds are named systematically by chain length (e.g., C10) and by the position of the substituent on the chain (e.g., position 2)] to a major sulfophenyl carboxylate [SPC; here 3-(4-sulfophenyl)butyrate (3-C4-SPC)] and two minor products, namely, the α,β-unsaturated SPC (SPC-2H, here 3-C4-SPC-2H) and the SPC+2C (here 5-C6-SPC) species (D. Schleheck, T. P. Knepper, K. Fischer, and A. M. Cook, Appl. Environ. Microbiol. 70:4053-4063). The degradation of centrally substituted congeners by strain DS-1 was examined in this work. 5-C10-LAS yielded not only the predicted 4-C8-SPC, 4-C8-SPC-2H, and 6-C10-SPC (about 70% of products) but also sulfophenyl dicarboxylates (SPdC), i.e., C6-, C8-, and C10-SPdC. These were identified by electrospray ionization-mass spectrometry (ESI-MS) after separation by high-pressure liquid chromatography (HPLC). ESI ion-trap MS and ESI-time of flight-MS were used to confirm the identities of key intermediates. Different mixtures of congeners obtained by separation of commercial LAS by HPLC were degraded, and the degradative products were compared. If a congener carried the sulfophenyl substituent on the 5, 6, or 7 position, SPdCs were formed as well as SPC, SPC-2H, and SPC+2C, whereas the substituent on the 2, 3, or 4 position yielded only SPC, SPC-2H, and SPC+2C. Some 50 products were generated from the 20 LAS congeners: 11 major SPCs, each with an SPC-2H and an SPC+2C (i.e., 33 SPC and SPC-2H species), and about 17 SPdC species. A large array of compounds, many in low quantities, is thus generated by P. lavamentivorans DS-1 during the degradation of commercial LAS.

Linear Arrays of Helical Polyribosomes in Cells Exposed to Antitumor Drug Vincristine Sulfate

1969 ◽  
Vol 27 ◽  
pp. 358-359
Author(s):  
Awtar Krishan
Keyword(s):  
Close Association ◽  
Annulate Lamellae ◽  
Large Array ◽  
Vincristine Sulfate ◽  
Linear Arrays ◽  
Golgi Membranes ◽  
Related Drug ◽  
Drug Leads ◽  
Lethal Doses ◽  
Vinblastine Sulfate

Earle's L-929 fibroblasts treated with mitosis-arresting but sub-lethal doses of vinblastine sulfate (VLB) show hypertrophy of the granular endoplasmic reticulum and annulate lamellae. Exposure of the cells to heavier doses of vincristine sulfate (VCR), a VLB-related drug, leads to the accumulation of large amounts of helical polyribosomes, Golgi membranes and crystals in the cytoplasm. In many of these cells a large number of helical polyribosomes are arranged in prominent linear rows, some of which may be up to 5 micrometers in length. Figure 1 shows a large array of helical polyribosomes near a crystalline mass (CRS) in an Earle's L-929 fibroblast exposed to VCR (5ϒ/ml.) for 3 hours At a higher magnification, as seen in figure 2, the helical polyribosomes are seen arranged in parallel rows. In favorably cut sections, a prominent backbone like "stalk" of finely granular material, measuring approximately 300Å in width is seen in close association with the linear rows of helical polyribosomes.

Chelation-assisted transition metal-catalysed C–H chalcogenylations

2020 ◽  
Vol 7 (8) ◽  
pp. 1022-1060 ◽  
Author(s):  
Wenbo Ma ◽  
Nikolaos Kaplaneris ◽  
Xinyue Fang ◽  
Linghui Gu ◽  
Ruhuai Mei ◽  
...  
Keyword(s):  
Transition Metal ◽  
Recent Advances ◽  
Site Selectivity ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

This review summarizes recent advances in C–S and C–Se formations via transition metal-catalyzed C–H functionalization utilizing directing groups to control the site-selectivity.

EFFECT OF NICOTINE ON SEXUAL BEHAVIOUR OF MUTANT STRAIN (CURLED) OF DROSOPHILLA MELANOGASTER

2018 ◽  
Vol 24 (1) ◽  
Author(s):  
SHAMIM AKHTER CHOUDHARY
Keyword(s):  
Mutant Strain ◽  
Sexual Behaviour ◽  
Virgin Female ◽  
P Value ◽  
Pooled Data ◽  
Mating Latency ◽  
Males And Females ◽  
Food Medium ◽  
Food Media ◽  
Dose Dependent

In the present study, an attempt was made to study the effect of plant extract on Sexual behaviour of Mutant Strain (Curled) of Drosophila melanogaster. The LC50 has been estimated with 1% of the food media. The virgin females and males were isolated and fed with normal food media for three days. Then sub-lethal concentrations of 0.625 μl / 100 ml food, 1.2 μl /100 ml food, 2.5μl /100 / food of nicotine were mixed in food medium and allowed in flies to feed for two days. Then appropriate combination of untreated / treated males and females were introduced into the mating chamber. Courtship latency, mating latency and copulation duration were studied. After observation of the behaviour, mated flies were allowed to produce progeny. The sexual behaviour of bachelor male and virgin female obtained in the progeny was also studied. The pooled data were analyzed by student t-test and the result indicates p-value significant at 0.05 levels. The courtship latency was affected by in treatment but it is neither dose dependent nor sex dependent.

Three-Component [1+1+1] Cyclopropanation with Ruthenium(II)

2018 ◽  
Author(s):  
Tanner C. Jankins ◽  
Robert R. Fayzullin ◽  
Eugene Khaskin
Keyword(s):  
Quaternary Carbon ◽  
Poor Control ◽  
One Step ◽  
Synthetic Routes ◽  
Mechanistic Investigations ◽  
Chiral Centers ◽  
Metal Catalyzed ◽  
The Right ◽  
Substituted Cyclopropanes

We report a one-step, Ru(II)-catalyzed cyclopropanation reaction that is conceptually different from the previously reported protocols that include Corey-Chaykovsky, Simmons-Smith, and metal catalyzed carbene attack on olefins. Under the current protocol, various alcohols are transformed into sulfone substituted cyclopropanes with excellent isolated yields and diastereoselectivities. This new reaction forms highly congested cyclopropane products with three new C–C bonds, three or two new chiral centers and one new quaternary carbon center. 22 examples of isolated substrates are given. Previously reported synthetic routes for similar substrates are all multi-step, linear routes that proceed with overall low yields and poor control of stereochemistry. Experimental mechanistic investigations suggest initial metal-catalyzed dehydrogenation of the alcohol substrate and catalyst independent stepwise attack of two equivalents of sulfone on the aldehyde under basic conditions. While the Ru(II) is only responsible for the initial dehydrogenation step, the rate of aldehyde formation is crucial to maintaining the right balance of intermediates needed to afford the cyclopropane product.

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