Value-added oil and animal feed production from corn-ethanol stillage using the oleaginous fungus Mucor circinelloides.

This study highlights the potential of oleaginous fungus, Mucor circinelloides in adsorbing/assimilating oil and nutrients in thin stillage (TS), and producing lipid and protein-rich fungal biomass. Fungal cultivation on TS for 2 days in a 6-L airlift bioreactor, resulted in a 92% increase in oil yield from TS, and 20 g/L of fungal biomass (dry) with a lipid content of 46% (g of oil per 100g dry biomass). Reduction in suspended solids and soluble chemical oxygen demand (SCOD) in TS were 95% and 89%, respectively. The polyunsaturated fatty acids in fungal oil were 52% of total lipids. Fungal cells grown on Yeast Malt (YM) broth had a higher concentration of γ-linolenic acid (17 wt.%) than those grown on TS (1.4 wt.%). Supplementing TS with crude glycerol (10%, v/v) during the stationary growth phase led to a further 32% increase (from 46% to 61%) in cellular oil content.

Tetrabutylammonium fluoride (TBAF)-catalyzed addition of substituted trialkylsilylalkynes to aldehydes, ketones, and trifluoromethyl ketones.

Herein we report that tetrabutylammonium fluoride (TBAF) is a very efficient catalyst for the addition of trialkylsilylalkynes to aldehydes, ketones, and trifluoromethyl ketones in THF solvent at room temperature. The reaction conditions are mild and operationally simple, and a variety of aryl functional groups, such as chloro, trifluoromethyl, bromo, and fluoro groups, are tolerated. Impressively, using our protocol, useful CF(3)-bearing tertiary propargylic alcohols can be synthesized. Product yields are generally better than or comparable to those in the literature. 1-Phenyl-2-trimethylsilyl acetylene, trimethyl ((4-(trifluoromethyl)phenyl)ethynyl)silane, 1-trimethylsilyl-1-hexyne, and trimethyl(thiophen-3-ylethynyl)silane underwent clean conversion to their corresponding propargylic alcohols as products under our conditions. Heterocyclic carbonyl compounds, such as furan-3-carboxaldehyde, thiophene-3-carboxaldehyde, and 2-pyridyl ketone, gave good yields of propargylic alcohols.

P[N(i-Bu)CH(2)CH(2)](3)N: nonionic Lewis base for promoting the room-temperature synthesis of α,ß-unsaturated esters, fluorides, ketones, and nitriles using Wadsworth-Emmons phosphonates.

The bicyclic triaminophosphine P(RNCH(2)CH(2))(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,ß-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.

P(PhCH2NCH2CH2)3N catalysis of Mukaiyama aldol reactions of aliphatic, aromatic, and heterocyclic aldehydes and trifluoromethyl phenyl ketone.

Herein we find that proazaphosphatrane 1c is a very efficient catalyst for Mukaiyama aldol reactions of aldehydes with trimethylsilyl enolates in THF solvent. Only the activated ketone 2,2,2-trifluoroacetophenone underwent clean aldol product formation with a variety of trimethylsilyl enolates under similar conditions as the aldehydes. The reactions were carried out at room temperature using (1-methoxy-2-methyl-1-propenyloxy)trimethylsilane, whereas the temperature was -15 degrees C in the case of 1-phenyl-1-(trimethylsilyloxy)ethylene. The reaction conditions are mild and operationally simple, and a variety of aryl functional groups, such as nitro, amino, ester, chloro, trifluoromethyl, bromo, iodo, cyano, and fluoro groups, are tolerated. Product yields are generally better than or comparable to those in the literature. 1-Phenyl-1-(trimethylsilyloxy)ethylene, 1-(trimethylsilyloxy)cyclohexene, and 2-(trimethylsilyloxy)furan underwent clean conversion to beta-hydroxy carbonyl compounds under our reaction conditions. In the case of bulky (2,2-dimethyl-1-methylenepropoxy)trimethylsilane, only alpha,beta-unsaturated esters were isolated. Heterocyclic aldehydes, such as pyridine-2-carboxaldehyde, benzofuran-2-carboxaldehyde, benzothiophene-2-carboxaldehyde, and 1-methyl-2-imidazolecarboxaldehyde, gave good yields of Mukaiyama products. An optimized synthesis for the catalyst 1c is also reported herein.

P(PhCH(2)NCH(2)CH(2))(3)N: an efficient lewis base catalyst for the synthesis of propargylic alcohols and Morita-Baylis-Hillman adducts via aldehyde alkynylation.

Proazaphosphatrane P(PhCH(2)NCH(2)CH(2))(3)N (1a) is an efficient catalyst for the addition of aryl trimethylsilyl alkynes to a variety of aromatic, aliphatic, and heterocyclic aldehydes in THF at room temperature. The reaction conditions are mild and employ a low catalyst loading (ca. 5 mol %). Only propargylic alcohols were isolated in good to excellent isolated yields when electron-rich, electron-neutral, heterocyclic, and aliphatic aldehydes were employed, whereas beta-branched Morita-Baylis-Hillman (MBH) type adducts were isolated with electron-deficient aromatic aldehydes after conventional acid hydrolysis of the TMS ether products. Alkynes containing heterocyclic and aromatic groups bearing electron-withdrawing or -donating substituents underwent clean addition to cyclohexanecarboxaldehyde and to electron-rich aromatic aldehydes to give propargylic alcohols in excellent isolated yields. beta-Branched Morita-Baylis-Hillman (MBH) type adducts were isolated when electron-deficient aromatic aldehydes were employed. Reaction pathways to both types of products are proposed.