Protecting manipulation

With the exception of the diol 9, that was obtained from the corresponding aldehyde in up to 35% yield, most of the chiral diols mentioned above were isolated in yields of only 20-25%. The formation of the acyloin-type condensation products is in competition with the much more efficient reduction of the carbonyl carbon and saturation of the double bond of the unsaturated aldehydes that were used as substrates. We became interested in the mode of reduction of particular aldehydes such as 54-56 (Scheme 8) in a study of the total synthesis of natural a-tocopherol (vitamin E) (23). We expected to obtain chiral alcohols that would be useful for conversion into natural isoprenoids from the reduction of the a-double bond of the above aldehydes. Indeed, 54-56 afforded up to 75% yield of the saturated carbinols 57-59 by treatment with yeast. Whereas the ee of 57 and 58 was ca 85%-90%, that of 59 is 99%, as shown by NMR experiments on the (-)-MTPA derivative (24). The synthetic significance of carbinol 59 was based on the structural unit present in natural isoprenoids (see brackets in structural formulas). This protected synthon can be unmasked by ozonolysis, as indicated by the high yield conversion of 59 into (S)-(-) -3-methyl-y-butyrolactone 60 (Scheme 9). Product 59 is a bifunctional chiral intermediate which does not need protective manipulation in that... 

Now roll up the Carius tube (while still in a vertical position) in a strip of ordinary thick drying paper, and then place it in the heavy iron protector tube if the Carius tube is too short and tends to disappear within the iron tube, a short section of old glass tubing should first be placed in the iron tube so that the capillary of the Carius tube just projects. The function of the paper is to protect the Carius tubing from being scratched, and also (more important) to prevent the local overheating which would otherwise occur at places where the Carius tube is in direct contact with the iron tube. The sealed tube, throughout its manipulation, should be left as nearly vertical as possible, so that the contents do not leave the rounded end. 

Personnel who must work in areas in which tritium contamination exceeds permitted levels are safeguarded by protective clothing, such as ventilated plastic suits. Detailed descriptions of laboratories suitable for manipulation of tritium can be found in Reference 9. 

Selective and Override Control When there are more controlled variables than manipulated variables, a common solution to this problem is to use a selector to choose the appropriate process variable from among a number of available measurements. Selec tors can be based on either multiple measurement points, multiple final control elements, or multiple controllers, as discussed below. Selectors are used to improve the control system performance as well as to protect equipment from unsafe operating conditions. 

FIG. 8 50 Manipulating heat flow linearizes the loop and protects against variations in supply temperature. 

Alkyds are the most widely used protective-coatings at 1-million pounds annual world consumption. Brittle and insoluble in common solvents, they are manufactured with a plasiici/m. -Manipulating the molecular structure produces alkyds with the desirable properties. 

Bu2SnO, benzene BnBr, DMF, heat, 80% yield. This method has also been used to protect selectively the anomeric hydroxyl in a carbohydrate derivative. The replacement of Bu2SnO with Bu2Sn(OMe)2 improves the process procedurally. The use of stannylene acetals for the regioselective manipulation of hydroxyl groups has been reviewed. ... 

The construction of the five contiguous stereocenters required for a synthesis of compound 3 is now complete you will note that all of the substituents in compound 5 are positioned correctly with respect to the carbon backbone. From intermediate 5, the completion of the synthesis of the left-wing sector 3 requires only a few functional group manipulations. Selective protection of the primary hydroxyl group in 5 as the corresponding methoxymethyl (MOM) ether, followed by benzylation of the remaining secondary hydroxyl, provides intermediate 30 in 68 % overall yield. It was anticipated all along that the furan nucleus could serve as a stable substi-... 

The completion of the synthesis of key intermediate 2 requires only a straightforward sequence of functional group manipulations. In the presence of acetone, cupric sulfate, and camphorsulfonic acid (CSA), the lactol and secondary hydroxyl groups in 10 are simultaneously protected as an acetonide (see intermediate 9). The overall yield of 9 is 55 % from 13. Cleavage of the benzyl ether in 9 with lithium metal in liquid ammonia furnishes a diol (98% yield) which is subsequently converted to selenide 20 according to Grie-co s procedure22 (see Scheme 6a). Oxidation of the selenium atom... 

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