Advanced Synthesis & Catalysis
10.1002/adsc.201900342
allylic phosphates with (pin)B–B(dan) under copper
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catalysis.
Diverse allyl–B(dan) derivatives are
straightforwardly accessible from //-substituted
allylic phosphates, preparable readily from respective
allylic alcohols, and furthermore the hydroboration of
allyl–B(dan) provides diborylpropanes with different
boron-Lewis acidity, whose less Lewis acidic boron
moiety (B(dan)) can selectively be transformed into a
nitrogen functionality. Further studies on the Chan–
Lam–Evans-type coupling of dan-substituted
organoboranes as well as the catalytic B(dan)-
installing reactions are in progress.
[
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Typical Procedure for the Copper-Catalyzed B(dan)-
Installing Allylic Borylation Using (pin)B–B(dan) (1a)
and Allyl Phosphate (2e) (Table 2, Entry 5)
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A flame-dried Schlenk tube equipped with a magnetic
stirring bar was charged with SIMesCuCl (2.0 mg, 5.0
2 3
mol), THF (1.0 mL) and Cs CO (48.9 mg, 0.15 mmol)
under an argon atmosphere. Then, the mixture was stirred
at room temperature for 15 min before addition of allyl
diethyl phosphate 2e (19.4 mg, 0.10 mmol) and (pin)B–
B(dan) 1a (58.8 mg, 0.20 mmol). After the mixture was
stirred at 30 °C for 2 h, the mixture was diluted with ethyl
acetate and the organic solution was filtered through a
Celite pad. Evaporation of the solvent followed by silica
gel-column chromatography (hexane:ethyl acetate = 2:1 as
an eluent) gave 3e as a red oil; yield: 18.9 mg (91%).
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Acknowledgements
This work was financially supported by JSPS KAKENHI Grant
Numbers JP16H01031 in Precisely Designed Catalysts with
Customized Scaffolding and JP17K05864. The authors also
acknowledge Tonen General Sekiyu Research/Development
Encouragement
& Scholarship Foundation and for their
generous financial assistance.
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