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Highly diastereo- and enantioselective syntheses of 1,5-disubstituted (E)-1,5-anti-pent-2-endiols 1 and (Z)-1,5-syn-pent-2-endiols 2 have been achieved via the one-pot coupling of two different aldehydes with either (E)-gamma-(1,3,2-dioxaborinanyl)-allyl]diisopinocampheylborane (4) or (E)-gamma-(4,4,5,5-tetraphenyl-1,3,2-dioxaborolanyl)allyl]diisopinocampheylborane (11), respectively. The indicated diols 1 and 2 are obtained in 63-95% yield with 89-96% ee and >/=20:1 diastereoselectivity in all cases. The bifunctional gamma-boryl-substituted allylborane reagents 4 and 11 were generated in situ by the hydroboration of allenes 3 and 10 with diisopinocampheylborane. The keys to the success of this method are the excellent stereocontrol in the allylboration step leading to 5 and the corresponding substituted methallylboronate derived from 11, the stereospecificity of the subsequent allylboration reaction of the substituted methallylboronate intermediates, and the ability of the diol auxiliary to induce equatorial or axial placement of the substituent alpha to boron in transition states 7 and 8.

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[structure: see text] A synthesis of the C(1)-C(25) fragment of amphidinol 3 is described. The synthesis features two applications of double allylboration reaction methodology for the highly stereoselective synthesis of 1,5-diol units in the C(1)-C(15) segment.