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. 2017 Aug 17;73(33):5011-5017.
doi: 10.1016/j.tet.2017.05.068. Epub 2017 May 20.

Practical, efficient, and broadly applicable synthesis of readily differentiable vicinal diboronate compounds by catalytic three-component reactions

Suttipol Radomkit  1 , Zhenxing Liu  1 , Anna Closs  1 , Malte S Mikus  1 , Amir H Hoveyda  1
Affiliations

Practical, efficient, and broadly applicable synthesis of readily differentiable vicinal diboronate compounds by catalytic three-component reactions

Suttipol Radomkit et al. Tetrahedron. .

Abstract

A practical, efficient and broadly applicable catalytic method for synthesis of easily differentiable vicinal diboronate compounds is presented. Reactions are promoted by a combination of PCy3 or PPh3, CuCl and LiOt-Bu and may be performed with readily accessible alkenyl boronate substrates. Through the use of an alkenyl-B(pin) (pin = pinacolato) or alkenyl- B(dan) (dan = naphthalene-1,8-diaminato) starting material and commercially available (pin)B- B(dan) or B2(pin)2 as the reagent, a range of vicinal diboronates, including those that contain a B-substituted quaternary carbon center, may be prepared in up to 91% yield and with >98% site selectivity. High enantioselectivities can be obtained (up to 96:4 er) through the use of commercially available chiral bis-phosphine ligands for reactions that afford mixed diboronate products.

Keywords: Allylic substitution; Boron; Catalysis; Copper; Enantioselective synthesis; Vicinal diboron compounds.

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Figures

Scheme 1
Scheme 1
Related previous work and the basis for the present studies.
Scheme 2
Scheme 2
Reactions with 2-substituted allylic phosphates. See the Supporting Information for experimental and analytical details.
Scheme 3
Scheme 3
Functionalization through chemoselective oxidation and cross-coupling. See the Supporting Information for experimental and analytical details.
Scheme 4
Scheme 4
Functionalization through catalytic Z-selective cross-metathesis reactions. See the Supporting Information for experimental and analytical details.
Scheme 5
Scheme 5
Catalytic enantioselective variants. For 3, 1.5:1 ratio of vinyl– B(pin): allylphosphate was used; see the Supporting Information for experimental and analytical details.
See this image and copyright information in PMC

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