Electrocydic reactions photochemical

Electrocydic reactions, then, are completely stereospecific. The exact stereochemistry depends upon two things (a) the number of double bonds in the polyene, and (b) whether reaction is thermal or photochemical. It is one of the triumphs of the orbital symmetry approach that it can account for all these facts indeed, most of the examples known today were predicted by Woodward and Hoffmann before the facts were known. 

Photochemical electrocycltc ring-closure in a 4-electron system works well for many acyclic dienes (2.17) and related cyclic systems 12.18). The situation with conjugated trienes is more complex, and they can act as 6-electron systems (2.19) leading to cydohexa-1,3-dienes, or as 4-electron systems (2.20) giving cyclobutenes. In addition they can undergo other photochemical reactions such as geometrical isomerization about the central double bond Iwhich must be c/s if a 6-electron electrocydic ring-closure is to take place). 

An important group of conjugated diene/triene systems are those in the vitamin D series. The key reactions in the commercial manufacture of vitamin D (and probably also in its formation in skin exposed to daylight) are a photochemical, conrotatory electrocydic ring-opening in the provitamin, and a thermal 1.7-shift of hydrogen in the previtamin so formed (2.23). High conversions to the vitamin are not normally possible because all three species absorb appreciably at the... 

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