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. 2017 May 15;56(21):5806-5811.
doi: 10.1002/anie.201702107. Epub 2017 Apr 18.

Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts

Carolina M Avila  1 , Jigar S Patel  1 , Yernaidu Reddi  2 , Masato Saito  1 , Hosea M Nelson  1   3 , Hunter P Shunatona  1 , Matthew S Sigman  4 , Raghavan B Sunoj  2 , F Dean Toste  1
Affiliations

Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts

Carolina M Avila et al. Angew Chem Int Ed Engl. .

Abstract

A mild, asymmetric Heck-Matsuda reaction of five-, six- and seven-membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd0 and chiral anion co-catalysts, the latter functioning as a chiral anion phase-transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by-products. More specifically, BINAM-derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP-D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway.

Keywords: Heck reaction; Heck-Matsuda reaction; chiral anions; palladium; phase-transfer catalysis.

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Figures

Figure 1
Figure 1
Optimized transition state geometries for (a) reductive elimination and (b) isomerization of 11 in the presence of chiral phosphates at the SMD(Toluene)/B3LYP-D3/6-31G**, LANL2DZ(Pd) level of theory. The distances are in Å. Only selected hydrogen atoms are shown for improved clarity. C=black, O=red, H=gray, N=cyan, P=blue and Pd=green.
Scheme 1
Scheme 1
Heck–Matsuda reaction and enantioselective variants.
Scheme 2
Scheme 2
Enantioselective Heck–Matsuda reaction via chiral anion phase t ransfer catalysis.
Scheme 3
Scheme 3
Arylation of Cycloheptene 16.
Scheme 4
Scheme 4
Enantioselective synthesis of amino acid 20.
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