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. 2007 Dec 7;72(25):9772-5.
doi: 10.1021/jo701633k. Epub 2007 Nov 14.

Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes

José G Roman  1 , John A Soderquist
Affiliations

Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes

José G Roman et al. J Org Chem. .

Abstract

Simple Grignard procedures provide methallylboranes 1a and 1b in enantiomerically pure form from air-stable precursors in 98% and 95% yields, respectively. These reagents add smoothly to aldehydes and methyl ketones, respectively, providing branched 2 degrees- (6, 69-89%, 94-99% ee) and 3 degrees- (10, 71-87%, 74-96% ee) homoallylic alcohols.

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Figures

Figure 1
Figure 1
Proposed models for the most energetically favorable pre-transition state complexes which explain the observed stereochemistry in the methallylboration of RCHO with 1a (A) and RCOMe with 1b (B).
Scheme 1
Scheme 1
Preparation of Methallylborane 1.
Scheme 2
Scheme 2
Asymmetric Allylboration of Aldehydes with 1a.
Scheme 3
Scheme 3
Asymmetric Allylboration of Benzaldimine with 1a.
Scheme 4
Scheme 4
Asymmetric Allylboration of Ketones with 1b.
Scheme 5
Scheme 5
Ozonolysis of β-Methyl Homoallylic Alcohols.
See this image and copyright information in PMC

References

    1. Herold T, Hoffmann RW. Angew Chem, Int Ed Engl. 1978;17:768.Herold T, Schrott C, Hoffmann RW. Chem Ber. 1981;114:359.Hoffmann RW, Herold T. Chem Ber. 1981;114:375.Brown HC, Jadhav PK, Perumal PT. Tetrahedron Lett. 1984;25:5111–5114.Brown HC, Jadhav PK, Perumal PT. J Org Chem. 1986;51:432.Masamune S, Short RP. J Am Chem Soc. 1989;111:1892.See also: Ramachandran PV. Aldrichimica Acta. 2002;35:23. and ref. cited therein.Flamme EM, Roush WR. J Am Chem Soc. 2002;124:13644.Yakelis NA, Roush WR. J Org Chem. 2003;68:3838.Gao X, Hall DG. J Am Chem Soc. 2003;125:9308.Morgan JB, Morken JP. Org Lett. 2003;5:2573.Barrett AGM, Braddock DC, de Koning PD, White AJP, Williams DJ. J Org Chem. 2000;65:375.Barrett AGM, Beall JC, Braddock DC, Flack K, Gibson VC, Salter MM. J Org Chem. 2000;65:6508.Corey EJ, Yu C, Kim SS. J Am Chem Soc. 1989;111:5495.Brown HC, Racherla US, Liao Y, Khanna VV. J Org Chem. 1992;57:6608.

    1. Wu TR, Shen L, Chong JM. Org Lett. 2004;6:2701. - PubMed
    2. Keck GE, Krishnamurthy D. Org Syn. 1998;75:12.
    3. Yamamoto H, Ishiba A, Nakashima H, Yanagisawa A. J Am Chem Soc. 1996;118:4723.
    4. Soai K, Niwa S. Chem Rev. 1992;92:833.
    5. Loh TP, Zhou JR, Li XR. Tetrahedron Lett. 1999;40:9333.
    6. Pu L, Yu HB. Chem Rev. 2001;101:757. - PubMed
    7. Pu L. Tetrahedron. 2003;59:9873.
    8. Denmark SE, Fu J. Chem Rev. 2003;103:2763. - PubMed

    1. Walsh PJ, Kim JG, Camp EH. Org Lett. 2006;7:4413.See also: Källström S, Jagt Rb, Sillanpää R, Feringa BL, Minnaard AJ, Leino R. Eur J Org Chem. 2006:3826.

    1. Nelson SG, Cheung SW, Kassick AJ, Hilfiker MA. J Am Chem Soc. 2002;124:13654. - PubMed
    2. De Brabander JK, García-Fortanet J, Jiang X. J Am Chem Soc. 2005;127:11254. - PubMed
    3. Nakada M, Suzuki T, Inoue M. J Am Chem Soc. 2003;125:1140. - PubMed

    1. Burgos CH, Canales E, Matos K, Soderquist JA. J Am Chem Soc. 2005;127:8044.(b) Available from Sigma-Aldrich, Inc.

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