Total synthesis of (±)-15-deoxyprostaglandin E₁

Stereospecific Conjugate Alkenyl Group Transfer to α,β-Enones Using Vinylalane Reagents

“…Several subsequent reports corroborating these results and providing additional interesting applications and extensions of this methodology have appeared, including examples illustrating that the stereochemistry of unsaturation in the organocopper reactant is retained in the product (2)(3)(4)(5). This outcome is also contingent on other prior important observations that retention of double bond geometry is preserved, both in: (i) converting precursor alkenyl halide to the corresponding lithio species (6,7), and (ii) trans- 'Holder of a 1967 Science Scholarship.…”

Synthesis And Novel Stereochemical Results In The Lithium–Ammonia Reduction Of Some 4-Alkyl-Δ1(9)-2-octalones

“…Furthermore, in the case of each of the octalones 7-11, the presence of an axially oriented alkyl group at C4 would tend to sterically hinder hydrogenation from the cr side. In the event, hydrogenation of compounds 7-11 in 0.3 N ethanolic potassium hydroxide over palladium-on-charcoal afforded, in each case, a high yield (295%) of product which consisted nearly entirely (294%) of the corresponding cis-fused 2-decalone (27)(28)(29)(30)(31). In each case, the minor ( 1 6 % ) hydrogenation product exhibited g.1.c.…”

“…It should be noted that recently, subsequent to the time at which the above-described work was carried out, there have appeared a number of reports concerning the use of lithium divinylcuprate (25)(26)(27)(28)(29) and related reagents (30)(31)(32)(33)(34)(35)(36)(37)(38)(39)(40) in conjugate addition to a variety of u,p-unsaturated ketones.…”

“…This material was shown to be homogeneous by g. 1 [3,4~,4a~-Trimethyl-cis-3,4,4a,5,6,7,8, Octalone 9 was subjected to hydrogenation under conditions identical with those described previously for the preparation of decalone 27. From 100 mg of octalone 9 there was obtained 96 mg (96%) of an oil which was shown by g. I [3,4a[3-dimethyl-cis-3,4,4a,5,6,7,8,8aoctahydro-2(1 H) -naphthalenone (31) This compound was prepared by hydrogenation of octalone 11 via a procedure identical with that described for the preparation of decalone 27. From 100 mg of octalone 11 there was obtained 96 mg (95%) of a n oil which exhibited one component by g. .…”

L‐Ascorbate, a strong inducer of L‐dopa (3,4‐dihydroxy‐L‐phenylalanine) production from pre‐grown mycelia of Aspergillus oryzae NRRL‐1560

“…To obtain a consistent product quality, the operating variables must not be altered. However, changes in product yield may arise from deviation in specified transfer routes or variation in the impurities of the medium [7]. The inherent non-linearity of L-dopa production renders its control difficult, so there is a need to fine-tune the process by intelligent control.…”