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. 2010 Nov 5;12(21):4892-5.
doi: 10.1021/ol1020515.

Allyl transfer to aldehydes and ketones by Brønsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines

Maureen K Reilly  1 , Scott D Rychnovsky
Affiliations

Allyl transfer to aldehydes and ketones by Brønsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines

Maureen K Reilly et al. Org Lett. .

Abstract

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).

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Figures

Figure 1
Figure 1
Relationship between rate of allylation and concentration of acid.
Figure 2
Figure 2
Possible allyl transfer reagent generated under the reaction conditions.
Figure 3
Figure 3
Calculated Transitions States 1,3,2-oxazaborolidine from 25 (left) and 1,3,2,6-dioxazaborocane from 26 (right).
See this image and copyright information in PMC

References

    1. Denmark SE, Fu J. Chem Rev. 2003;103:2763–2794. - PubMed
    2. Hatano M, Ishihara K. Synthesis. 2008;11:1647–1675.
    3. Lachance H, Hall DG. Org React. 2008;73:1–554.
    1. Keck GE, Tarbet KH, Geraci LS. J Am Chem Soc. 1993;115:8467–8468.
    2. Teo Y-C, Goh J-D, Loh T-P. Org Lett. 2005;7:2743–2745. - PubMed
    1. Kinnaird JW, Ng PY, Kubota K, Wang X, Leighton JL. J Am Chem Soc. 2002;124:7920–7921. - PubMed
    2. Kubota K, Leighton JL. Angew Chem, Int Ed. 2003;42:946–948. - PubMed
    3. Hackman BM, Lombardi PJ, Leighton JL. Org Lett. 2004;6:4375–4377. - PubMed
    1. Roush WR, Walts AE, Hoong LK. J Am Chem Soc. 1985;107:8186–8190.
    2. Brown HC, Jadhav PK. J Am Chem Soc. 1983;105:2092–2093.
    3. Corey EJ, Yu CM, Kim SS. J Am Chem Soc. 1989;111:5495–5496.
    4. Burgos CH, Canales E, Matos K, Soderquist JA. J Am Chem Soc. 2005;127:8044–8049. - PubMed
    5. Canales E, Prasad KG, Soderquist JA. J Am Chem Soc. 2005;127:11572–11573. - PubMed
    6. Kanai M, Wada R, Shibuguchi T, Shibasaki M. Pure Appl Chem. 2008;80:1055–1062.
    7. Lou S, Moquist PN, Schaus SE. J Am Chem Soc. 2006;128:12660–12661. - PubMed
    8. Barnett DS, Moquist PN, Schaus SE. Angew Chem, Int Ed. 2009;48:8679–8682. - PMC - PubMed
    1. Kennedy JWJ, Hall DG. J Am Chem Soc. 2002;124:11586–11587. - PubMed
    2. Yu SH, Ferguson MJ, McDonald R, Hall DG. J Am Chem Soc. 2005;127:12808–12809. - PubMed
    3. Rauniyar V, Hall DG. J Am Chem Soc. 2004;126:4518–2519. - PubMed
    4. Hall DG. Pure Appl Chem. 2008;80:913–927.
    5. Rauniyar V, Zhai H, Hall DG. J Am Chem Soc. 2008;130:8481–8490. - PubMed

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