1. Asymmetric Suzuki–Miyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin Yasuhiro Uozumi Angew. Chem. Int. Ed. 2009, 48, 2708 –2710

3. (a) Avoiding cis/trans isomerizations after the oxidative addition step (b) Limited flexibility around N-N bonds, providing an adequate chiral environment and a considerable steric crowding beneficial for the formation of the 14e Pd(0) catalysts and the for reductive elimination step Rosario Ferna´ndez J. AM. CHEM. SOC. 2008, 130, 15798–15799

5. a Isolated yield. b Conditions: (A) excess 2 (1.5 equiv); (B) excess 1(2.5 equiv). e The absolute configuration was assigned by comparison with literature data: see ref 6h. g Reaction performed in 1 mL of solvent. h The absolute configuration was assigned after demethylation to the 1-(biphenyl-2-yl)naphthalen-2-ol derivative and comparison of the optical rotation with the reported value.

7. J. Am. Chem. Soc. 2001, 123, 2919 - 2920

9. Tetra-n-butylammonium fluoride or TBAF is a quaternary ammonium salt with the chemical formula (CH 3 CH 2 CH 2 CH 2 ) 4 N + F -. In the laboratory the compound is usually encountered in the latter form as a source of organic-soluble fluoride ion to remove silyl ether protecting groups. It is also used as a phase transfer catalyst and as a mild base.

10. [a] Reactions were carried out in water at 80 o C for 24 h with the reaction components in the following ratio: 1 (mol)/2 (mol)/TBAF (mol)/Pd-(OAc) 2 (mol)/PS–PEG–L* (mol of P)/H2O (L)= 1 : 5 : 10 : 0.1 : 0.1 : 20. [b] Yield of the isolated product. [c] The ee value was determined by HPLC (chiralpak OD-H or AD-H). The absolute configuration is shown in parenthesis. [d] After crystallization

11. Conclusions The highly enantioselective Suzuki–Miyaura biaryl coupling was carried out in water for the first time with a recyclable palladium complex of a chiral imidazoindole phosphine ligand supported on an amphiphilic PS–PEG resin. In this article, the asymmetric Suzuki–Miyaura coupling for the synthesis of a variety of axially chiral biaryl compounds with high stereoselectivity (up to 94%ee).