Biosynth: Homebrewing Ephedrine

[Shooting_Star]

Since this same subject came up in the Crystal Meth forum, ressurecing this seems worthwhile. 

My questions on the matter are:
Since both the precursor and the product (along with the side reaction products) are toxic to the biomass, is there perhaps some way to periodically rinse the yeast so as to refresh them and keep them viable?

Perhaps some sort of filtering to remove the nascent liquor for processing out the ephedrine, then returning the yeast to the fermenttion vessle to continue eating, reproducing and makeing more gold?

This one really seems like a good way to keep a low profile whilst continuing to cook.

(BTW, while vaginal yeas may be a strain of Candida, it is C albicans, not C. utilis)

burn-out only occurs if you go too fast in the wrong direction

[Organikum]

Yeast & L-PAC

Look up:
WO 90/04631
US 6,271,008
WO 01/44486
US 5,173,413
DE 518029 (german)
GB 365535

all at:

http://ch.espacenet.com/espacenet/ch/en/e_net.htm

more to follow, if someone cares

ORGY
(who seeks for a bee experienced in catalytic hydrogenation/red. alkylation for putting together parts fitting so easily. Has done research on yeast not only in theory and now... PM!)
"I hope I'm becoming more eccentric. More room, you know.
 More room in the brain."

[Organikum]

Sorry in thy above post was a typo:
Thy german patent is:
DE1518029
it is identical with
GB1118293

whoooo not one noticed it.
seems me and my ketoalcohol will stay thy lonesome riders...
...no! Not all alone.

Shop closed.
ORGY

"I hope I'm becoming more eccentric. More room, you know.
 More room in the brain."

[Organikum]

Yes we proudly present, thy neverbefore shown image of thy mysterious

EPHEDRINE BIOSYNTH

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000199197-file_f5do.jpg" title="View this image">


A Pic, a pic, a pic!
As nobody wants to read patents nowadays (P-SAM ya thy guilty one ya did it intentional confess!   )

Hey look, thats what it looks like, hold it before it undergoes racemisation! Oh, too late, its only PAC, no L-PAC anymore.

For those searching for valid information before starting thy part of free phantasting this may be helpful.

WO 90/04631

enough is enough
ya´ll get no colored one.

ORGY



"I hope I'm becoming more eccentric. More room, you know.
 More room in the brain."

[java]

I read the posting and I have also tried to understand the reading on Biotransformation for L-ephedrine  Production.  by P.L. Rogers,H.S. Shin and B. Wang  found in the pub lished by Springer on volume 56  Advances in Biochemical Engineering Biotechnology

First in the use of Candida Utilis,  the max growth occured at PH 7   while the RQ( respiratory quotient ) value = 4   this value being the O2 AND CO2 concentration  and the relative stirring of the metabolic step of the production. 

While the article is good  the data ca be confusing , also they use equipment  out of reach for many of us.
However  I would like to post the whole article for the interpretation of the reader , since many may not have access  to the original work.

I would like to know if this would be cool or does it go against some type of policy of the forum ?  The Journal that contains the article is pricy $150 dol. but its info is worth it.

[ballzofsteel]

Dont know if its cool or not,but I shure would like to catch a glimpse of that.Ive searched briefly on the net for it but only keep coming up with the same few paragraphs,telling me that it can be done and the basic procedure,not going into any specific detail.
Any info or links would be much appreciated by me.

Im pretty sure it would be cool to post some of it at least.
 
Its not on rhodiums page yet is it?

I realy think,seeing as the C.M board seems to have dried up when it comes to novel or new ideas and how the OTC sources of feedstock are becoming more of a bitch every day,that this subject should be the focus of all the meth bees.
Im sure within a couple of months we could get it cracked and form a relatively OCT method for biosynthimg e.
Then all we would have to worry about is when big brother makes yeast available by presription and starts regulating sugar purchases.

Whadda ya say bees?This would be one huge battle won in this war of ours.

BIOBALLZ

Then we just gotta get flinger to let us in on how to grow  his meth plants and were laughing.

[java]

I wasn't able to post the whole refrence to the P.L.Rogers- H.S. Shin, B. Wang......BIOTRANSFORMATION FOR L- EPHEDRINE
so I sent it to the forum moderator see where he puts it, I also sent it to Rhodium maybe they will post it in its
entirety..................Question , is it possible to use fructose sugar  as the source ?  or just  raw sugar cane sugar?

Here is recent finding , I thought it was interesting:


1: Biotechnol Bioeng  2001 Aug 20;74(4):317-25

Continuous production of (R)-phenylacetylcarbinol in an enzyme-membrane reactor
using a potent mutant of pyruvate decarboxylase from Zymomonas mobilis.

Goetz G, Iwan P, Hauer B, Breuer M, Pohl M.

Institut fur Enzymtechnologie der Universitat Dusseldorf im Forschungszentrum
Julich, D-52426 Julich, Germany.

The optimization of a continuous enzymatic reaction yielding
(R)-phenylacetylcarbinol (PAC), an intermediate of the L-ephedrine synthesis, is
presented. We compare the suitability of three pyruvate decarboxylases (PDC),
PDC from Saccharomyces cerevisiae, PDC from Zymomonas mobilis, and a potent
mutant of the latter, PDCW392M, with respect to their application in the
biotransformation using acetaldehyde and benzaldehyde as substrates. Among
these, the mutant enzyme was the most active and most stable one. The reaction
conditions of the carboligation reaction were investigated by determining
initial rate velocities with varying substrate concentrations of both aldehydes.
From the resulting data a kinetic model was inferred which fits the experimental
data with sufficient reliability to deduce the optimal concentrations of both
substrates for the enzymatic process. The results demonstrate that the
carboligation is most efficiently performed using a continuous reaction system
and feeding both aldehydes in equimolar concentration. Initial studies using a
continuously operated enzyme-membrane reactor gave (R)-PAC with a space-time
yield of 81 g L(-1). d(-1) using a substrate concentration of 50 mM of both
aldehydes. The yield was easily increased by cascadation of enzyme-membrane
reactors. The new strategy allows the synthesis of (R)-PAC from cheap substrates
in an aqueous reaction system. It thereby overcomes the limitation of by-product
formation that severely limits the current fermentative process.

PMID: 11410856 [PubMed - indexed for MEDLINE]

most recent article found and lots of research stuff on biotransformation at:

http://www3.ncbi.nlm.nih.gov/htbin-post/Entrez/query?db=0&form=1&term=biotransformation+for+L-ephedrine

......good reading

[Rhodium]

Sent it to me? Resend it please - rhodium@ziplip.com

[Organikum]

what thy heck frucose?
I cannot say it will not work, but never heard about.

what thy yeast needs: vitamines, minerals its a lifeform.

happa, happa for yeast:
starting fermentation broth: molasses + yeast extract(does RECYCLING say anything to ya?) + glucose aka dextrose aka fucking plain sugar.
+ ceremony of sacrifice at choice.

it´s all in thy patents

hungry yeast is bad yeast
ORGY

"I hope I'm becoming more eccentric. More room, you know.
 More room in the brain."

[Rhodium]

Here is the  document I got from Java:

https://www.thevespiary.org/rhodium/Rhodium/archive/biotransformation.ephedrine.pdf

[MMM]

It is unlikely you could use Fructose.  It may depend on the strain of yeast being used, but in brewing of drinkable stuff Fructose is added to sweeten the drink as it is unfermentable by the std yeasts used.  Tastes twice as sweet as sugar, and one hell of a lot better than the artificial gunk.
When sugar is added, the yeast produces an enzyme which breaks sugar (sucrose) into Fructose and Glucose.  The Glucose is then fermented to alcohol.

HTH, MMM
When the day is bad,and life's a curse
CHEER UP!!! Tomorrow may be Worse!!
('HAGAR' Comic)

[Organikum]

MMM you are absolutely right.
Glucose = Dextrose but not Sucrose.
My thought was, that plain sugar can be supplied to feed the yeast, but as Dextrose is cheap and available this may be taken.
If betacyclodextrin is added it is possible to apply more benzaldehyde and better yields are reached.  The adding of about 10% ethylalcohol may be substituted for betacyclodextrin.



thanks MMM
ORGY

[Jetson]

any new updates or breaks on this subject?  jetson thought this had died long ago but to his surprise the last reply was just last april.     jetson's going to do some independant studying and will post anything new he finds but most likely it'll be more catching up than anything. 
^{the devil is so lonely}

[Organikum]

have a look at this quite new abstract and hope this sophisticated techniques will soon serve the clandestine chemist in his daily fight.

© Springer-Verlag 2002

Original Paper

Enzymatic (R)-phenylacetylcarbinol production in benzaldehyde emulsions

B. Rosche1, , N. Leksawasdi1, V. Sandford1, M. Breuer2, B. Hauer2 and P. Rogers1

(1)
School of Biotechnology and Biomolecular Sciences, University of New South Wales, Sydney NSW 2052, Australia

(2)
BASF-AG, Hauptlaboratorium, 67056 Ludwigshafen, Germany

Abstract. (R)-Phenylacetylcarbinol [(R)-PAC)] is the chiral precursor for the production of the pharmaceuticals ephedrine and pseudoephedrine. Reaction conditions were improved to achieve increased (R)-PAC levels in a simple batch biotransformation of benzaldehyde emulsions and pyruvate, using partially purified pyruvate decarboxylase (PDC) from the filamentous fungus Rhizopus javanicus NRRL 13161 as the catalyst. Lowering the temperature from 23°C to 6°C decreased initial rates but increased final (R)-PAC concentrations. Addition of ethanol, which increases benzaldehyde solubility, was not beneficial for (R)-PAC production. It was established that proton uptake during biotransformation increases the pH above 7 thereby limiting (R)-PAC production. For small-scale studies, biotransformations were buffered with 2-2.5 M MOPS (initial pH 6.5). High concentrations of MOPS as well as some alcohols and KCl stabilised PDC. A balance between PDC and substrate concentrations was determined with regards to (R)-PAC production and yields on enzyme and substrates. R. javanicus PDC (7.4 U/ml) produced 50.6 g/l (337 mM) (R)-PAC in 29 h at 6°C with initial 400 mM benzaldehyde and 600 mM pyruvate. Molar yields on consumed benzaldehyde and pyruvate were 97% and 59%, respectively, with 17% pyruvate degraded and 24% converted into acetaldehyde and acetoin; 43% PDC activity remained, indicating reasonable enzyme stability at high substrate and product concentrations.



E-mail: B.Rosche@unsw.edu.au
Phone: +61-2-93853895
Fax: +61-2-93136710

some perhaps valuable information on L-PAC:

L-PAC, aka laevo-phenylacetylcarbinol, is also named:

1-hydroxy-1-phenyl-2-propanone
1-hydroxy-1-phenylpropanone
l-1-phenylpropan-1-ol-2-on (phenylpropanolon)    -> old german
laevo-phenylpropanolone
1-phenyl-2-ketoalcohol-(1)
1-phenyl-propanol-1-one-2
R-PAC

I am sure the babylonians have still more names for this simple compound. If somebody finds another one - PM me.

Also is this molecule well known since 1921, and heavily used in pharmaceutic industry, but there is no entry at chemfinder or another public database I have access.

Please, somebody who has access to better resources could look up the properties (boiling point, soluble in...)? Post them here or/and PM me?
THANKS!
Racemisation in basic solution is very fast, thats what I could dig up.

IMHO biotransformations are a sharp sword in the hand of clandestine chemistry. And I don´t speak of genetically engineered or otherwise dangerous organisms. All day everywhere yeasts are keeping a widely undeveloped (or not published) power of transformation. Enzyme extraction isn´t rocket science also.

I will be happy if I would get the L-PAC properties
ORGY

~ Love is the law, love under will. ~

[Organikum]

I found some more data for L-PAC:

Formula         C9H10O2
Composition         C, 71.98; H, 6.71; O, 21.31
Mol. Weight       150.1745
Exact Mass          150.06808

and the CAS NR is:  90-63-1


if now somebody with STN or BEILSTEIN access, AFAIK anyone living in GB and most people on universities have this for example, could be so kind and look this up and post the properties of L-PAC?

thanks
ORGY


app. 30 seconds after a synth is posted they will come and show you all the goodies with the wise smile and this "we knew all this for long, boy" expression. Lot of Yogis here. Teacherism.

~ Love is the law, love under will. ~

[lugh]

1-hydroxy-1-phenylacetone, aka Acetylphenylcarbinol, boils at 205-7° C at atmospheric pressure, 135-7° C at 24 mm Hg, 140-5° C at 11 mm Hg and 66° C at .2 mm Hg    It's miscible with most organic solvents, and more information can be found in JCS 1232 (1930), Ann 484 1 (1930), Compt Rend 198 1998 (1934), Biochem Z 245 238 (1932) & 230 320 (1931) and Bull Soc Chim 43 573 (1928)    

Phenylacetylcarbinol, aka 1-hydroxy-3-phenylacetone has a melting point of 48° C and boils at 144-5° C at 12-13 mm Hg, and more information can be found in Compt Rend 197 1328 & 1649 (1933)      

[java]

Organikum  Post No 388164 and there after.......that should have been here , and so it is now!.

[roger2003]

Industrial Biotransformation:

http://www.ct.utwente.nl/ipp/docs/Papersparasu/2001_SPKP.pdf

http://imb.usal.es/castellano/personales/rss/SchmidetalEnzymes2002.pdf

[placebo]

I apologise if any of this has already been posted....

Here is the relevant bits from the SchmidetalEnzymes2002.pdf in the above post...

The flavoenzyme tryptophan 7-halogenase has been evaluated for selective chlorination of tryptophan and indole derivatives. The reaction is thought to proceed via the formation of an epoxide and ring-opening to a chlorohydrin followed by dehydration. Glaxo Wellcome Research and Development reported on the use of nucleoside oxidase. The enzyme was found to have a very broad substrate spectrum towards unnatural nucleosides.

Immobilization of the oxidase directly from crude extracts onto Eupergit-C resulted in stabilization of its activity, which also allowed reuse of the enzyme and an easy scale-up of the reaction. An interesting carbon–carbon bond formation reaction was reported for the preparation of (R)-phenylacetylcarbinol by carboligation of pyruvate and benzaldehyde using various pyruvate decarboxylases. Continuous production of (R)-phenylacetylcarbinol from acetaldehyde and benzaldehyde could be achieved using a mutant of pyruvate decarboxylase from Zymomonas mobilis in an enzyme membrane reactor (EMR) with space-time yields of 81g L–1 d–1.

Widespread application of enzymes in the chemical industry will depend on the ability to couple enzymatic and chemical steps. Chemoenzymatic reaction sequences profit from the high technical development level of both chemical and enzymatic reactions. DSM uses well-established amidase catalysis to produce enantiopure Cá-tetrasubstituted á-amino acids containing terminal double bonds that react to cyclic oligopeptides by Grubbs olefin metathesis. Lonza uses a sequence of nitrile hydratase catalysis, chemical hydrogenation, and amidase-catalyzed reactions to obtain enantiopure pipecolic and piperazine carboxylic acids from aromatic nitrile precursors. Making biocatalysis compatible with chemical multistep synthesis is one of the important future challenges for this new technology.

Conclusions
Today, applications of enzymes in the chemical industry are already well established and, given the current developments, the number of biocatalytic processes will continue to increase rapidly. The first hurdle, confidence in the new technology, has been taken and as more and more processes, technology and infrastructure are implemented, efforts in biocatalytic research and development will also increase. This will allow the discovery and application of new enzymes and biological counterparts for traditional chemical reactions and will facilitate the integration of enzymatic steps in chemical multistep syntheses.

Biotransformation processes for L-PAC production
Prof Peter Rogers

Biotransformation processes involving both yeast (Candida utilis) and pyruvate decarboxylase (PDC) are being evaluated for the production of L-phenylacetylcarbinol (L-PAC) from substrates benzaldehyde and pyruvate. L-PAC is an intermediate in the production of the decongestant and antiasthmatic pharmaceuticals, ephedrine and pseudoephedrine. Kinetic models for the process are under development together with a computer-based optimal substrate feeding profile for benzaldehyde.

Funding sources: Commercial (ICI 1994-6; other 1997-9)
Student involvement: One Postdoctoral Research Fellow and two PhD students, MAppSc and Honours students

Recent publications:
Shin, H.S. and Rogers, P.L. (1996) Production of L-PAC from benzaldehyde using partially purified pyruvate decarboxylase (PDC). Biotechnol. Bioeng. 49, 52-62.

Shin, H.S. and Rogers, P.L. (1996) Kinetic evaluation of biotransformation of benzaldehyde to L-PAC by immobilized pyruvate decarboxylase. Biotechnol. Bioeng. 49, 429-436.

Rogers, P.L., Shin, H.S. and Wang, B. (1997) Biotransformation for L-ephredrine production. Adv. Biochem. Eng. 56, 33-60.

Liew, M.K.H., Fane, A.G. and Rogers, P.L. (1997) Fouling effects of yeast culture with antifoam agents on microfilters. Biotechnol. Bioeng. 53, 10-16.

Liew, M.K.H., Fane, A.G. and Rogers, P.L. (1997) Fouling of microfiltration membranes by broth-free antifoam agents. Biotechnol. Bioeng. 56, 89-98.

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000199197-file_rmd6.jpg" title="View this image">

http://www.biotech.unsw.edu.au/research2.htm

http://www.iupac.org/publications/ci/1997/november/review.pdf

Here is the details from this one...

Environmental biotechnology

The November issue also contains selected proceedings of an International Conference on Environmental Biotechnology '96 held in Palmerston North, New Zealand, 1–4 September 1996. The published conference papers offer a wide-ranging analysis of the potential of biotechnology to waste treatment, specific perspectives on environmental damage and remediation, industrial research on pollutant mitigation, research into the area of upflow anaerobic sludge blanket reactors, the biological treatment of food industry wastes and two examples of cleaner technology for developments from the pharmaceutical and paper industries. The cleaner technology examples included production of phenylacetylcarbinol (PAC) and production of phenylacetylcarbinol by yeast through productivity improvements and waste minimisation. LPhenylacetylcarbinol is a precursor for the synthesis of L-ephedrine and D-pseudoephedrine, two pharmaceuticals with nasal decongestant properties. LPhenylacetylcarbinol is generated biologically through the pyruvate decarboxylase-mediated condensation of added benzaldehyde with acetaldehyde generated metabolically from feed stock sugars via pyruvate. Some of the added benzaldehyde is converted through the action of alcohol dehydrogenase(s) to benzyl alcohol, an undesired by-product.

L-Phenylacetylcarbinol extracted from the fermentation broth is converted chemically by hydroamination in the presence of methylamine and hydrogen to L-ephedrine, and then by isomerization to D-pseudoephedrine. Bruce Anderson and colleagues at the Royal Melbourne Institute of Technology present a dual approach strategy to enhance the ratio of product to by-product generated and to minimize the waste treatment burden of the spent fermentation broth. He explains that benzaldehyde delivery to the fermentation has been modified to ensure that sufficient raw material is available, together with pyruvate, during peak periods of pyruvate decarboxylase activity, and that benzaldehyde is less available during periods of high alcohol dehydrogenase activity. The inorganic content of the spent fermentation broth has been reduced substantially by the partial substitution of raw sugar for molasses in the medium, with a reduction of molasses content by 60% resulting in an increase of phenylacetylcarbinol production.

Further work on the optimization of the concentration of carbohydrate, nitrogen and phosphate in the fermentation has been conducted and has led, he claims, to further productivity increases, together with reduced waste generation, resulting in an L-phenylacetylcarbinol process which is considerably 'cleaner' than the parent process.

Taken from some guy's resume I found in a search engine...

Head, Food & Fermentation Technology Division.

The project dealt with the biotransformation of benzaldehyde to L- phenyl acetyl carbinol (synthon for various drugs) using yeast isolate. Various aspects like standardization of the method of analysis, purification and identification of product & byproducts of the biotransformation using various techniques were standardised. Using  yeast isolate, various process parameters for increasing yield of the product and reusability of the biocatalyst were studied. A novel immobilization method for the aforesaid biotransformation was standardised and the process parameters using immobilized cell system studied. The mass transfer coefficient, power consumption and hold up in a stirred tank reactor with a dual impeller system were studied for the growth and biotransformation medium and were compared with those for air-water system.

After establishing the correlation between these operating parameters, a scaling up of this  biotransformation to 5 L was achieved in a systematic manner. Work was also carried out on the synthesis of various chiral compounds using a combination of chemical synthesis and  biotransformation using Rhizopus arrhizus.

to be continued.

[placebo]

From

http://www.swsbm.com/Abstracts/Ephedra-AB.txt

*****ADVANCES IN BIOCHEMICAL ENGINEERING/BIOTECHNOLOGY*****
Rogers PL  Shin HS  Wang B 
Biotransformation for L-ephedrine production.
In: Adv Biochem Eng Biotechnol (1997) 56:33-59
ISSN: 0724-6145

L-ephedrine is widely used in pharmaceutical preparations as a decongestant and anti-asthmatic compound. One of the key intermediates in its production is L-phenylacetylcarbinol (L-PAC) which can be obtained either from plants (Ephedra sp.), chemical synthesis involving resolution of a racemic mixture, or by biotransformation of benzaldehyde using various yeasts. In the present review, recent significant improvements in the microbial biotransformation are assessed for both fed-batch and continuous processes using free and immobilised yeasts. From previous fed-batch culture data, maximal levels of L-PAC of 10-12 gl-1 were reported with yields of 55-60% theoretical based on benzaldehyde. However, recently concentrations of more than 22 gl-1 have been obtained using a wild-type strain of Candida utilis. This has been achieved through optimal control of yeast metabolism (via microprocessor control of the respiratory quotient, RQ) in order to enhance substrate pyruvate production and induce pyruvate decarboxylase (PDC) activity.

Processes involving purified PDC have also been evaluated and it has been demonstrated that L-PAC levels up to 28 gl-1 can be obtained with yields of 90-95% theoretical based on the benzaldehyde added. In the review the advantages and disadvantages of the various strategies for the microbial and enzymatic production of L-PAC are compared. In view of the increasing interest in microbial biotransformations, L- PAC production provides an interesting example of enhancement through on-line control of a process involving both toxic substrate (benzaldehyde) and end-product (L-PAC, benzyl alcohol) inhibition.

Registry Numbers:
EC 4.1.1.1 (Pyruvate Decarboxylase)
100-52-7 (benzaldehyde)
299-42-3 (Ephedrine)
67-64-1 (Acetone)
90-63-1 (1-hydroxy-1-phenyl-2-propanone)

Taken from

http://www.ephedra.nu/engels/

Also found same info mirrored here...

http://www.r00t-access.org/texts/ephedrine.html

First site is interesting site devoted completely to ephedrine.

Synthesis of ephedrine
======================

Actively fermenting yeast transforms benzaldehyde into L-phenylacetylcarbinol (L-PAC), which can be reductively aminated to afford ephedrine or phenypropa-nolamine (depending on the amine used)
---------------------------------------------------------------------------

Title: ISOLATION, ANALYSIS, AND SYNTHESIS OF EPHEDRINE AND ITS DERIVATIVES

Abstract: A review is given of methods for the isolation, quantitative determination, and modification of the ephedrine alkaloids, and advances in this field of natural compound chemistry.

Author: Gazaliev, A. N.; Zhurinov, M. Zh.; Fazylov, S. D.; Balitskii, S. N.
Reference: Chem.Nat.Compd.(Engl.Transl.), 25, 3, 1989, 261-271
--------------------------------------------------------------------------

Title: The biosynthesis of ephedrine

Abstract: It is shown by 13C nuclear magnetic resonance spectroscopy that the labelled C2 fragment of <2,3-13C2>pyruvic acid is transferred intact into the C-methyl group and the adjacent carbon atom of the Ephedra alkaloids, norephedrine, ephedrine, norpseudoephedrine, and pseudoephedrine, in growing plants of Ephedra gerardiana.This finding serves to identify pyruvate as the elusive precursor of the aliphatic C2 terminus of the skeleton of the alkaloids.In earlier experiments with 14C-labelled substrates, label from <3-14C>pyruvic acid was incorporated mainly, but not exclusively, into the C-methyl group of ephedrine, and label from <2-14C>pyruvate was incorporated similarly into the carbon atom adjacent to the C-methyl group.A C6-C1 unit related to benzaldehyde or benzoic acid has long been known to generate the benzylic fragment of the carbon skeleton of the Ephedra alkaloids.It is likely that the carbon skeleton of ephedrine is generated from pyruvate and either benzaldehyde or benzoic acid, by a reaction analogous to the formation of acetoin or diacetyl from pyruvate and acetaldehyde or acetic acid, respectively.Key words: biosynthesis of ephedrine, Ephedra alkaloids, 13C NMR spectra, ephedrine, biosynthesis of pyruvic acid, incorporation into ephedrine 13C NMR spectra.

Grue-Sorensen et al, Can.J.Chem., EN, 67, 1989, 998-1009
--------------------------------------------------------------------------------

Stereoselectrive Syntheses of Ephedrine and Related 2-Aminoalcohols of High Optical Purity from Protected Cyanohydrins

Abstract: Ephedrine and related optically active b-aminoalcohols can be prepared by zinc borohydride reduction of aryl O-protected magnesium imines and aryl a-hydroxyimimes which in turn are readily available from optically active cyanohydrins.

Jackson et al, Tetrahedron Lett., 31, 10, 1990, 1447-1450
-------------------------------------------------------------------------

Title: SYNTHESIS OF EPHEDRINE (DIALKYL PHOSPHOROTHIOATE)S. CRYSTALLOGRAPHIC STRUCTURE OF EPHEDRINE (DIETHYL PHOSPHOROTHIOATE)

Abstract: The synthesis of ephedrine (dialkyl phosphorothioate)s has been effected.The method of their preparation and their properties are described.The IR and PMR spectra of ephedrine (dialkyl phosphorothioate)s and some results of an x-ray structural investigation of the spatial structure of ephedrine (diethylphosphorothioate) are given.
-----------------------------------------------------------------------

Methods for Biocatalyst Screening
http://www.google.com/search?q=cache:mMkB389mue4C:link.springer-ny.com/link/service/series/0010/papers/2074/20740001.pdf+1-hydroxy-1-phenyl-2-propanone&hl=en&ie=UTF-8

Again, sorry if some is redundant, I tried to check everything back thru this thread, but it's a bit of a mission. It seems as though the limited amount of info on the net regarding this matter is mostly the same stuff.