The Reduction of Simple Olefins with Sodium and Methanol in Liquid Ammonia¹

Chapter 22 Synthesis and Biophysical Characterization of Stabilized α‐Helices of BCL‐2 Domains

“…After the synthesis of the bis-alkylated morpholinone, the chiral directing group is cleaved by reduction with lithium in liquid ammonia to yield the Boc-protected amino acid (S)-2-(tert-butoxycarbonylamino)-2-methyl-hept-6-enoic acid (9). Several methods exist for the cleavage of the C-N and C-O bonds in the morpholinone (Williams et al, 2003); however, dissolving metal reduction is the only method that is compatible with the compounds synthesized (Greenfield et al, 1954), as the alternative methods requiring reduction with H 2 and palladium on carbon or oxidation with sodium periodate or lead (IV) tetraacetate would destroy the terminal olefin needed for the crosslinking reaction. To complete the synthesis, the Boc-protecting group on the α-amine is converted to Fmoc to ensure compatibility with Fmoc solid-phase peptide synthesis.…”

Alkylation-reduction of carbonyl systems. IV. Convenient and selective synthesis of simple and complex aromatic hydrocarbons by phenylation-reduction of aldehydes and ketones

“…2-Phenyloctane (22). Treatment of 2-octanone (2) as described above yielded 22 (88%) as a colorless oil: ir (film) 3030, 2960, 2930, 1450, and 695 cm-1; nmr (60 MHz, CCD 7.18 (5 H, apparent s), 2.66 (1 H, apparent sextet, J -7 Hz), 1.83-1.38 (2 H, m), a doublet centered at 1.22 (3 H, d, J =7 Hz) superimposed on an apparent broad singlet with fine splitting centered at 1.24 (8 H, broad s), and a perturbed triplet centered at 0.87 (3 H, t); mass spectrum m/e (relative intensity) 190 (M+ 9), 175 (10), 105 (100), 91 (13), 77 (6), and 43 (6).…”

“…Treatment of 6-methyl-5-hepten-2-one (5) as described above yielded 25 (90%) as a colorless oil: ir (film) 3030, 2960, 2930, 1600, 1495, 1450, 750, and 690 cm"1; nmr (60 MHz, CC14) 7.21 (5 H, apparent s), 5.30-4.92 (1 H, m), 2.69 (1 H, apparent q, J = 7 Hz), a broad singlet at 1.68 (3 H, s) superimposed on a broad multiplet at 2.15-1.58 (4 H, m), 1.51 (3 H, broad s), and 1.23 (3 H, d, J = 7 Hz); mass spectrum m/e (relative intensity) 188 (M+, 3-Phenyl-4(8)-p-menthene (26). Treatment of (+)-pulegone (6) as described above yielded 26 (85%) as a colorless oil: ir (film) 3070, 3035, 2925, 1603, 1490, 1450, and 690 cm"1; nmr (100 MHz, CDC13) 7.37-6.98 (5 H, m), 4.13-4.00 (0.3 H, m Ph-CH-, equatorial proton), 3.84-3.60 (0.7 H, m, Ph-Cfl-, axial proton), ca.…”