Baldwin Report

The real difficulties with the biradical interpretation began with the stereochemical studies on the cyclopentene formation. Early work was carried out by Mazzochi and Tamburin and by Doering and Sachdev, then, in 1976, Andrews and Baldwin reported a study that allowed a complete stereochemical quadrisection of the vinylcyclopropane rearrangement of optically active trans, trans-l-methyl-2-propenylcyclopropane. The four stereoisomeric 3,4-dimethylcyclopentenes formed in this reaction (see Figure 23)... 

In unpublished attempts to investigate the ability of animals to utilize Schardinger dextrins, B. H. Thomas and D. French fed rats a diet in which a part of the carbohydrate was supplied by highly purified /3-dextrin. The animals refused to eat the test diet except in very small quantities and within a week all animals on the ration were dead. Postmortem examination did not reveal the cause of death. In unpublished work from General Foods, Inc., Dr. R. R. Baldwin reports that with rats stomach-fed a suspension of /3-dextrin in vegetable oil, similar though erratic results were found. 

Baldwin reported the detection of the [M-I]" ion in FAB mass spectra of synthetic cyclostellettamines obtained as iodide salts. Unequivocal proof of their structures was obtained by high resolution atomic pressure chemical ionisation (APCI)-MS experiments on the [M+H] pseudo-molecular ion of the corresponding uncharged bis-tethrahydropyridine obtained by reduction of cyclostellettamines [44]. 

In 1969, Ollis recognised that the rearrangement of ally lie ammonium and sulfonium y tides was a facile process of considerable synthetic interest, and Baldwin reported his generalization of the sigma-tropic rearrangement processes. Since then, numerous examples of the synthetic utility of ylidic rearrangements have been recorded in the chemical literature and this number is growing continuously. 

The second example was reported by Baldwin, Bulger and coworkers, and features the oxidation of a phenol initiating a cationic cyclization sequence to afford the natural product ( )-aculeatin D (7-12) [5], Thus, when the dihydroxyketone 7-8 is treated with PhI(02CCF3)2, a formal two-electron oxidation of the phenol moiety takes place, triggering a twofold cationic-based cyclization to furnish the desired ( )-aculeatin D [( )-7-12] in 19% yield, together with 43% of the isomer ( )-7-ll and the side product ( )-7-10 via the cation 7-9 (Scheme 7.3). 

Next to tetrahedral systems, trigonal systems are considered as reaction centres in Baldwin s rules. These predict that 3- to 1-exo-trig reactions are all favoured processes. Very accurate EM s have been reported by Bruice and Benkovic (1963) for intramolecular nucleophilic attack on carbonyl in [39] and [40]. When Ar is varied from C6H5 to p-NOzC6H4, the EM of [39]... 

We saw at the outset of this section that for sulfenic anhydrides the thiolsulfinate structure RS(0)SR was thermodynamically preferred over RSOSR. Perhaps it is therefore fitting to close it by mentioning a situation in which another isomeric structure, that of a thiosulfoxylate ROSSR, has been found to be preferred over thiolsulfinate. Baldwin et al. (1971) reported that the thiolsulfinate [21] isomerizes readily to thiosulfoxylate [22] (76). On the other hand, in the system lacking the methyl groups, [23]—[24], thiolsulfinate [231... 

Nefazodone is an SSRl with 5-HT2 antagonist properties. Nefazodone is licensed as an antidepressant in many countries, and the evidence for efficacy from placebo-controlled and reference-controlled studies does not suggest that this drug is associated with superior efficacy (Dillier 1982 R. Fontaine et al. 1994 Mendels et al. 1995 Rickels et al. 1994). The 5-HT2 antagonism does not appear to confer extra efficacy, which appears to be similar to that of SSRls. However, a beneficial effect on sleep and on anxiety symptoms of depression is reported. This may be attributable to 5-HT2 blockade, but some studies have demonstrated nefazodone s superior efficacy to SSRls. One attribute of nefazodone that may be related to 5-HT2 blockade is that it is associated with rather little in the way of sexual side effects. A direct comparison between nefazodone and sertraline reported significantly fewer sexual side effects with nefazodone [Baldwin 1996). 

Baldwin et al102 synthesized the Fe(II) complex of capped porphyrin 43. This Fe(II) porphyrin complex was reported to bind molecular oxygen in pyridine at 25 °C, the life of the oxygenated complex being about 20 h. 

An entirely different approach to specific dehydrogenation has been reported by R. Breslow39 and by J. E. Baldwin.4,1 By means of this approach it was possible, for example, to convert 3a-cholestanol (2) to 5a-cholest-14-en-Ja-ol (3). thus introducing a double bond... 

C—509 Propellant, See conf Report by R.A.Miller J.E.Baldwin, NOTS(Naval Ordnance Test Station) TP 2660(1962)... 

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