Battersby

The nitrile is described in a patent tChem. Abs.. 1955, 15963) the last stages were carried out by A. R. Battersby s research group at Cambridge. Chloromethylation is described in Tedder, Vol 2, p.213 and Norman P.372-3. 

The addition of large enolate synthons to cyclohexenone derivatives via Michael addition leads to equatorial substitution. If the cyclohexenone conformation is fixed, e.g. as in decalones or steroids, the addition is highly stereoselective. This is also the case with the S-addition to conjugated dienones (Y. Abe, 1956). Large substituents at C-4 of cyclic a -synthons direct incoming carbanions to the /rans-position at C-3 (A.R. Battersby, 1960). The thermodynamically most stable products are formed in these cases, because the addition of 1,3-dioxo compounds to activated double bonds is essentially reversible. 

The reaction conditions applied are usually heating the amine with a slight excess of aldehyde and a considerable.excess of 2d-30hydrochloric acid at 100 °C for a few hours, but much milder ( physiological ) conditions can be used with good success. Diols, olefinic double bonds, enol ethers, and glycosidic bonds survive a Pictet-Spengler reaction very well, since phenol and indole systems are much more reactive than any of these acid sensitive functional groups (W.M. Whaley, 1951 J.E.D. Barton, 1965 A.R. Battersby, 1969). 

W. I. Taylor and A. R. Battersby, eds.. Oxidative Coupling of Phenols, Marcel Dekket, New York, 1967. 

The study of the biosynthesis of vitamin B 2 is a saga whose resolution, due primarily to Battersby (80—83) and Scott (84,85), requited an effort on the same magnitude as the total synthesis. It was only when recent molecular biology tools became available to complement en2ymology, isotopic labeling, chemical synthesis, and spectroscopy that solution of this problem became possible. 

Other tests for the detection of amino functionalities on solid supports include the TNBS (2,4,6-trinitrobenzenesulfonic acid, picrylsulfonic acid) [Hancock and Battersby Anal Biochem 71 260 ]976], the DABITC [Shah et al. Anal. Commun. 34 325 7997] and the NF31 [Madder et al. Eur J Org Chem 2787 7999] tests. 

Battersby and coworkers have developed selective methods for total synthesis of chlorins on a model system, as shown in Scheme 10.15, in which the Michael addition of 5-f3-nittoethyl pyrrole to enone and reductive cyclizadon are used as key steps. "... 

Snow, R J, C J R Fcrokes, and A R Battersby J Chem Soc, Chem Comjnuji. 524 tlSO Ij MiyaShita, M, B Z E Awen,andA YoShikoShi Yettzi/ieriroii, 46, 756S NSSO ... 

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