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. 2010 Jun 18;12(12):2706-9.
doi: 10.1021/ol1007444.

Highly (E)-selective BF(3).Et(2)O-promoted allylboration of chiral nonracemic alpha-substituted allylboronates and analysis of the origin of stereocontrol

Ming Chen  1 , William R Roush
Affiliations

Highly (E)-selective BF(3).Et(2)O-promoted allylboration of chiral nonracemic alpha-substituted allylboronates and analysis of the origin of stereocontrol

Ming Chen et al. Org Lett. .

Abstract

Delta-methyl-substituted homoallylic alcohols 2 were prepared in 71-88% yield, E:Z >30:1 and 93% to >95% ee via BF(3).Et(2)O-promoted allylboration with alpha-Me-allylboronate 1. The origin of high (E)-selectivity is proposed.

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Figures

Figure 1
Figure 1
Competing transition states for carbonyl addition reaction of α-substituted allylboronates 3
Scheme 1
Scheme 1
Synthesis of Allylboronate 8
Scheme 2
Scheme 2
Synthesis of Allylboronate 1
Figure 2
Figure 2
Competing transition states for BF3-catalyzed aldehyde allylboration with α-methyl allylboronate 1
Figure 3
Figure 3
Competing transition states for BF3-catalyzed aldehyde allylboration with α-chloro allylboronates 13
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