Acetyl carbinol

Silk PJ, Macaulay JB (2003) Stereoselective Biosynthesis of Chloroarylpropane Diols by the Basidiomycete Bjerkandera adusta Exploring the Roles of Amino Acids, Pyruvate, Glycerol and Phenyl Acetyl Carbinol. FEMS Microbiol Lett 11243 1... 

The diazepinol (40) is readily obtained from ketone (10) with sodium borohydride and is converted back into 10 with A -bromoacetamide or by Oppenauer oxidation.32 In a similar manner 32 and the AT-acetyl derivative of 10 can be reduced to carbinols. Acylation of 40 or treatment of the reduction product of 32 with acetic acid gave the trans-annular oxide (41). The carbinol (40), the acetyl carbinol from 10, the oxide (41), and the diacetyl analog of 41 all undergo rearrangement with mineral acid to give the four furfurylhydrazines (42).32... 

D.39) 2-Propanone, 1-hydroxy-, l-hydroxypropan-2-one, hydroxyacetone, acetyl carbinol,... 

Schmalfuss H. and Barthmeyer H. (1932) Nachweis von Diacetyl und Methyl-acetyl-carbinol in Lebensmitteln. Z. Unters. Lebensm. 63, 283-8. 

Historically, the biocatalytic acyloin condensation was first observed by Liebig in 1913 during studies on baker s yeast [1460]. A few years later, Neuberg and Hirsch reported the formation of 3-hydroxy-3-phenylpropan-2-one (phenyl acetyl carbinol, PAC) from benzaldehyde by fermenting baker s yeast [1461]. Without knowledge on the actual enzyme(s) involved, this biotransformation assumed early industrial importance when it was shown that the acyloin thus obtained could be converted into (-)-ephedrine by diastereoselective reductive amination, a process which is still utilized in almost unchanged form at a capacity of 120 t/year [1462, 1463] (Scheme 2.199). Subsequent studies revealed that this yeast-based protocol can be extended to a broad range of aldehydes [1464, 1465]. 

CuHn< (u-Acetoxy-nonylaldehyd 2 II169. Dinropyl-acetyl-carbinol-acetat 2 II169. 0-0BrMthoxy>2.2.4-trimethyl.penten-(3). 

FIGURE 4.32 Ephedrine synthesis of phenyl-acetyl carbinol. 

Chen K, Yue N, Qiu W, Zheng J, Bao W, Xu L, Huang D, inventors Igcon Therapeutics Co., Ltd., assignee. Application of pyruvate decarboxylase in biologically synthesizing L-phenyl acetyl carbinol. CN 101078010.2007 Nov 28. 

Production of Other L-Acetyl Carbinols by Yeast Cells... 

S Ose, J Hironaka. Studies on Production of Phenyl Acetyl Carbinol by Fermentation. Proceedings of the International Symposium on Enzyme Chemistry, Tokyo and Kyoto, 2, 1957, pp 457-460. 

A propoxyphene-like analgesic which obeys the empirical morphine rule is pyrroliphene (101). A Mannich reaction involving pyrrolidine, formaldehyde and propiophenone gave amino ketone 99, which was converted to tertiary carbinol 100 by reaction with benzyl magnesium chloride reaction with acetyl... 

The prevalence of 17-ethynyl carbinols among the orally active 19-nor progestins can lead to the impression that this is a necessary group for activity. The good potency shown by a compound that possesses the 17-hydroxy 17-acetyl moiety more characteristic of the 19-methyl progestins indicates that the structure-activity relationship is not quite that narrow. One... 

The crude carbinol is acetylated and dehydrated by refluxing its solution in 1 1. of glacial acetic acid and 500 ml. of acetic anhydride for 1 hour. The solution is then concentrated to about 500 ml. by distillation. After cooling overnight, the crystalline 3,12-diacetoxy-5A or-cholanyldiphenylethylene is collected on a filter and washed with acetic acid. The yield is 95-105 g. (63.5-70.0%) of material melting at 154-157° (Note 5). This product is sufficiently pure to be used for the preparation of Mor-desoxycholic acid (p. 38) one crystallization from acetone gives white crystals which melt at 156-157.5° fully purified material melts at 159.5-160.5°. 

A chiral hydride complex, tentatively assumed to be 86, prepared by partially reacting LAH with (- )-N-methylephedrine (1 equivalent) and /V-ethylaniline (2 equivalents) was found to reduce 2-acetyl-5,8-dimethoxy-3,4-dihydronaphtha-lene (87) quantitatively to the (- )-carbinol (88) with 92% e.e. (94,95). Carbinol 88, which was obtained optically pure by recrystallization, could be converted to (/ )-(-)-2-acetyl-5,8-dimethoxy-l,2,3,4-tetrahydro-2-naphthol (89). The lat-... 

The transformation of lithio derivatives of dibenzothiophene into alkyl, alkenyl, hydroxyalkyl, formyl, acetyl, carboxylic acid, alkyl and arylsilyl, boronic acid, aryl and carbinol derivatives of dibenzothiophene is dealt with in the appropriate sections. In addition, the four mono-tritio derivatives of dibenzothiophene have been prepared from the corresponding lithio derivatives via hydrolysis with tritiated water (Section III, 0,2). ... 

---