Swzwzary Hydrolysis of aa-trehalose by the enzyme trehalase, prepared from Sarcophaga barbata, is shown to proceed with inversion of configuration at C-1 of one of the two glucose molecules released.
2. Each mevalonate was converted into cholesterol by a rat liver preparation. 3. Each cholesterol specimen was converted into androsta-l,4-diene-3,17-dione by incubation with Mycobacteriumphlei in the presencd of 2,2'-dipyridyl. Each specimen of androsta-l,4-diene-3,17-dione was converted into androsta-l,4-dien-3-one-l7-ethylene ketal.4. The samples of androsta-1,4-dien-3-one-17-ethylene ketal were each converted chemically into oestrones in which the methyl group at C-18 is the only carbon atom that originated from C-6 in mevalonolactone.5. The oestrone from (3RS)-[6-3H1 ,6-'4C]mevalonolactone was oxidised chemically to acetic acid which was converted into p-bromophenacyl acetate and the 3H/14C ratio was measured.6. There was no overall loss of tritium from the methyl group of acetic acid, as measured by determining the 3H/14C ratios of the p-bromophenacyl esters, when the synthetic and degradative procedures 1 -5 were tested with [3H,,2-'4C]acetic acid.7. The oestrones derived from the 6R and 6S-mevalonolactones were oxidised. The chiralities of the resulting acetates were determined by an established procedure whereby the acetates were converted into 2s-malates which were examined for loss of tritium on equilibration with fumarate hydratase.8. The oestrone from (3RS,6R)-[6-2Hl,6-3Hl,6-'4C]mevalonate gave acetic acid which was converted into 2s-malate that retained 68.6 % of its tritium after treatment with fumarate hydratase ; the configuration of this acetic acid was R. 9. The oestrone from (3RS,6S)-[6-2Hl,6-3Hl,6-'4C]mevalonate was oxidised to acetic acid which was converted into 2s-malate that retained 31.9 % of its tritium after treatment with fumarate hydratase; the configuration of this acetic acid was S. 30. There was no overall change in the configuration of a chiral methyl group between C-6 of mevalonate and C-18 of oestrone. It is concluded that the intramolecular migration of a chiral methyl group from C-15 in 2,3-oxidosqualene to C-13 in lanosterol is stereospecific and occurs with overall retention of configuration.The stereochemical synthesis and configurational assay of the chiral methyl group [1,2] have led to the elucidation of the substrate stereochemistry of many enzymic reactions. The chiral methyl has been used to study the stereochemistry of two types of biological [4,11]. The work described in this paper represents a novel use of the chiral methyl group to elucidate the stereochemistry
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