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. 2013 Aug 28;135(34):12908-13.
doi: 10.1021/ja4073436. Epub 2013 Aug 19.

Protecting group-free synthesis of 1,2-azaborines: a simple approach to the construction of BN-benzenoids

Eric R Abbey  1 , Ashley N Lamm, Andrew W Baggett, Lev N Zakharov, Shih-Yuan Liu
Affiliations

Protecting group-free synthesis of 1,2-azaborines: a simple approach to the construction of BN-benzenoids

Eric R Abbey et al. J Am Chem Soc. .

Abstract

The protecting group-free synthesis of a versatile 1,2-azaborine synthon 5 is described. Previously inaccessible 1,2-azaborine derivatives, including the BN isostere of phenyl phenylacetate and BN1 triphenylmethane were prepared from 5 and characterized. The structural investigation of BN phenyl phenylacetate revealed the presence of a unique NH-carbonyl hydrogen bond that is not present in the corresponding carbonaceous analogue. The methyne CH in BN triphenylmethane was found to be less acidic than the corresponding proton in triphenylmethane. The gram-quantity synthesis of the parent 1,2-azaborine 4 was demonstrated, which enabled the characterization of its boiling point, density, refractive index, and its polarity on the ET(30) scale.

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Figures

Figure 1
Figure 1
1,2-azaborine synthons 1-3. Non-removable groups are labeled red. Removable and functionalizable groups are labeled green.
Figure 2
Figure 2
Solvatochromic studies using Reichardt’s betaine dye.
Figure 3
Figure 3
ORTEP illustrations, with thermal ellipsoids drawn at the 35% probability level, and packing diagram of compound 14.
Figure 4
Figure 4
ORTEP illustration of N-Me-BN1-triphenylmethane 16 with thermal ellipsoids drawn at the 35% level.
Scheme 1
Scheme 1
Reported synthesis of the parent 1,2-dihydro-1,2-azaborine 4.
Scheme 2
Scheme 2
Summary of this work.
Scheme 3
Scheme 3
Synthesis of synthon 5.
Scheme 4
Scheme 4
Gram-scale synthesis of parent 1,2-azaborine 4.
Scheme 5
Scheme 5
Functionalization of synthon 5. Conditions: a) vinylMgBr, −30 °C Et2O; HCl, 62%; b) n-BuLi, −30 °C Et2O; HCl, 83%; c) MeLi, −30 °C Et2O; MeI, 49%; d) MeLi, −30 °C Et2O; TMSCl, 63%.
Scheme 6
Scheme 6
Reactions of in situ-generated B-Cl intermediate 12.
Scheme 7
Scheme 7
Synthesis and acid-base chemistry of 16.
See this image and copyright information in PMC

References

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