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. 2015 Jul 22;137(28):8932-5.
doi: 10.1021/jacs.5b05879. Epub 2015 Jul 9.

Negishi Cross-Coupling Is Compatible with a Reactive B-Cl Bond: Development of a Versatile Late-Stage Functionalization of 1,2-Azaborines and Its Application to the Synthesis of New BN Isosteres of Naphthalene and Indenyl

Alec N Brown  1 , Bo Li  1 , Shih-Yuan Liu  1
Affiliations

Negishi Cross-Coupling Is Compatible with a Reactive B-Cl Bond: Development of a Versatile Late-Stage Functionalization of 1,2-Azaborines and Its Application to the Synthesis of New BN Isosteres of Naphthalene and Indenyl

Alec N Brown et al. J Am Chem Soc. .

Abstract

The compatibility of the Negishi cross-coupling reaction with the versatile B-Cl functionality has been demonstrated in the context of late-stage functionalization of 1,2-azaborines. Alkyl-, aryl-, and alkenylzinc reagents have been utilized for the functionalization of the triply orthogonal precursor 3-bromo-1-(tert-butyldimethylsilyl)-2-chloro-1,2-dihydro-1,2-azaborine (2) to furnish new 2,3-substituted monocyclic 1,2-azaborines. This methodology has enabled the synthesis of previously elusive BN-naphthalene and BN-indenyl structures from a common intermediate.

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Figures

Figure 1
Figure 1
Normalized absorption (solid green trace) and emission (dotted green trace) spectra of 6 (1 × 10−5 M in cyclohexane) overlaid with the normalized absorption (solid black trace) and emission (dotted black trace) spectra of naphthalene. The photoluminescence quantum yield of 6 was determined in cyclohexane at room temperature. The quantum yield of naphthalene was taken from the literature.
Scheme 1
Scheme 1. Negishi Coupling in the Presence of a B–Cl Bond
Scheme 2
Scheme 2. Compound 3c as a Versatile Common Intermediate for the Synthesis of BN Heterocycles 5 and 6
Scheme 3
Scheme 3. Synthesis and ORTEP Plot of BN-Indenyl 5a
aThermal ellipsoids at the 35% probability level; H atoms and two THF molecules (coordinated to Li+) omitted for clarity.
Scheme 4
Scheme 4. Synthesis of the Parental BN-Naphthalene Isostere 6; Compounds Shown in Red Have Not Been Synthesized
See this image and copyright information in PMC

References

    1. For an overview of BN/CC isosterism, see: Bosdet MJD, Piers WE. Can. J. Chem. 2009;87:8. Campbell PG, Marwitz AJ, Liu S-Y. Angew. Chem. Int. Ed. 2012;51:6074. Wang X-Y, Wang J-Y, Pei J. Chem. - Eur. J. 2015;21:3528.

    1. For the synthesis of the parental structure, see: Marwitz AJV, Matus MH, Zakharov LN, Dixon DA, Liu S-Y. Angew. Chem. Int. Ed. 2009;48:973.

    1. Dewar MJS, Marr PA. J. Am. Chem. Soc. 1962;84:3782.

    1. For an overview of Dewar’s work, see: Fritsch AJ. Chem. Heterocycl. Compd. (Hoboken NJ U. S.) 1977;30:381.

    1. White DG. J. Am. Chem. Soc. 1963;85:3634.

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