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. 2014 Oct 8;136(40):14027-30.
doi: 10.1021/ja508815w. Epub 2014 Sep 23.

Stereospecific pd-catalyzed cross-coupling reactions of secondary alkylboron nucleophiles and aryl chlorides

Ling Li  1 , Shibin Zhao, Amruta Joshi-Pangu, Mohamed Diane, Mark R Biscoe
Affiliations

Stereospecific pd-catalyzed cross-coupling reactions of secondary alkylboron nucleophiles and aryl chlorides

Ling Li et al. J Am Chem Soc. .

Abstract

We report the development of a Pd-catalyzed process for the stereospecific cross-coupling of unactivated secondary alkylboron nucleophiles and aryl chlorides. This process tolerates the use of secondary alkylboronic acids and secondary alkyltrifluoroborates and occurs without significant isomerization of the alkyl nucelophile. Optically active secondary alkyltrifluoroborate reagents undergo cross-coupling reactions with stereospecific inversion of configuration using this method.

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Figures

Figure 1
Figure 1
Catalytic cycle and possible side reactions in the Pd-catalyzed cross-coupling reaction of optically active nucleophiles and aryl electrophiles.
Figure 2
Figure 2
(a) Synthesis of (S)-10 from (S)-3-phenylbutyric acid (S)-(9). (b) Suzuki coupling of (R)-7 and PhCl. (c) Synthesis of (S)-11 from (S)-9. (d) Suzuki coupling of (R)-8 and PhCl.
Figure 3
Figure 3
Use of (R)-7 and (R)-8 in stereospecific cross-coupling reactions with aryl and heteroaryl chlorides.
See this image and copyright information in PMC

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