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. 2016 Mar 2;138(8):2508-11.
doi: 10.1021/jacs.5b13174. Epub 2016 Feb 16.

Carbohydrate-Catalyzed Enantioselective Alkene Diboration: Enhanced Reactivity of 1,2-Bonded Diboron Complexes

Lichao Fang  1 , Lu Yan  1 , Fredrik Haeffner  1 , James P Morken  1
Affiliations

Carbohydrate-Catalyzed Enantioselective Alkene Diboration: Enhanced Reactivity of 1,2-Bonded Diboron Complexes

Lichao Fang et al. J Am Chem Soc. .

Abstract

Catalytic enantioselective diboration of alkenes is accomplished with readily available carbohydrate-derived catalysts. Mechanistic experiments suggest the intermediacy of 1,2-bonded diboronates.

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Conflict of interest statement

Notes

The authors declare no competing financial interests.

Figures

Figure 1
Figure 1
Diboration of 1-tetradecene catalyzed by 1 – 9. Yield and er data are of the diboration product after oxidation to the 1,2-diol.
Figure 2
Figure 2
(a) Cascade single-pot diboration/cross-coupling reactions. For 22, 24 and 25 X=Br; for 23 X=Cl. (b) Large scale and glove-box-free diboration reactions.
Figure 3
Figure 3
(a) Exchange experiments with B2neo2 and 1 or TBS-DHG. (b) Preparation and reactions of B2(1)2. (c) 1,1 versus 1,2 bonding modes in neutral diboron reagents.
Figure 4
Figure 4
(a) Calculated energetics of boronic ester exchange for neutral and ate complexes. Values in kcal/mol; calculations performed by DFT (M06-2X/6-31+G*; PCM solvation model with THF, Gaussian 09). (b) Calculated reaction mechanism for alkene diboration with B2(4)2. (c) Comparison of 1,1- versus 1,2-bonded transition state structures.
Scheme 1
Scheme 1
Prospective Catalytic Cycle for Alcohol-Catalyzed Alkene Diboration.
Scheme 2
Scheme 2
Preparation of TBS-DHG and DHR.a aReagents: (a) H2, Pd/C, EtOAc; (b) lipase from Candida ru-gosa, pH=7 buffer, acetone/iPr2O; (c) TBSCl, imidazole; (d) K2CO3, CH3OH.
See this image and copyright information in PMC

References

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