Stereoselective synthesis of umuravumbolide

An efficient stereoselective total synthesis of umuravumbolide has been developed. The key features of the synthesis include Jacobsen resolution, Wadsworth Emmons olefination and silyl-tethered ring closing metathesis.

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(S)-2-ButyloxiraneC6H12O[α]D25=-8.2 (c 1, CHCl3)Absolute configuration: (2S)

(S)-Hept-1-en-3-olC7H14O[α]D20=+9.3 (c 1.5, CHCl3)Absolute configuration: (3S)

(R)-5-(4-Methoxybenzyloxy)pent-1-en-3-olC13H18O3[α]D25=-19.1 (c 1.8, CHCl3)Absolute configuration: (3R)

(5R,9S)-7,7-Diisopropyl-1-(4-methoxyphenyl)-5,9-divinyl-2,6,8-trioxa-7-silatridecaneC26H44O4Si[α]D25=-36 (c 1.2, CHCl3)Absolute configuration: (5R,9S)

(R)-3-(((S)-Hept-1-en-3-yloxy)diisopropylsilyloxy)pent-4-en-1-olC18H36O3Si[α]D25=+13.4 (c 3, CHCl3)Absolute configuration: (3R,3S)

(R,Z)-Methyl 5-(((S)-hept-1-en-3-yloxy)diisopropylsilyloxy)hepta-2,6-dienoateC21H38O4Si[α]D25=-10.9 (c 1.2, CHCl3)Absolute configuration: (5S,3R)

(Z)-Methyl 4-((4R,7S)-7-butyl-2,2-diisopropyl-4,7-dihydro-1,3,2-dioxasilepin-4-yl)but-2-enoateC19H34O4Si[α]D25=-23.0 (c 1.3, CHCl3)Absolute configuration: (4R,7S)