Chiral SO/P hybrid ligands: an enantioselective switch in palladium-catalyzed asymmetric allylic etherifications

A variety of chiral tert-butanesulfinylphosphine ligands were prepared and applied to the palladium-catalyzed asymmetric allylic etherification of 1,3-diphenylpropenyl acetate with alcohols. Excellent yields and moderate enantioselectivities were obtained. The absolute configuration of the etherification products was evidently switched only through the position change of the substituent on the P-aryl groups.

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(R)-(2-(tert-Butylsulfinyl)-6-methoxyphenyl)diphenylphosphineC23H25O2PS[α]D20=+179 (c 0.1, CHCl3)Source of chirality: (R)-1-(tert-butylsulfinyl)-3-methoxybenzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)-5-methoxyphenyl)di-o-tolylphosphineC25H29O2PS[α]D20=+267 (c 0.134, CHCl3)Source of chirality: (R)-1-(tert-butylsulfinyl)-4-methoxybenzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)di-o-tolylphosphineC24H27OPS[α]D20=+351 (c 0.146, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)di-m-tolylphosphineC24H27OPS[α]D20=+237 (c 0.152, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)di-p-tolylphosphineC24H27OPS[α]D20=+289 (c 0.31, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)bis(2-fluorophenyl)phosphineC22H21F2OPS[α]D20=+307 (c 0.248, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)bis(4-fluorophenyl)phosphineC22H21F2OPS[α]D20=+255 (c 0.208, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R)-(2-(tert-Butylsulfinyl)phenyl)bis(4-methoxyphenyl)phosphineC24H27O3PS[α]D20=+241 (c 0.182, CHCl3)Source of chirality: (R)-(tert-butylsulfinyl)benzeneAbsolute configuration: (R)

(R,E)-(3-(Benzyloxy)prop-1-ene-1,3-diyl)dibenzeneC22H20O[α]D20=-13 (c 0.202, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((2-Fluorobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19FO[α]D20=-8 (c 0.158, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((2-Chlorobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19ClO[α]D20=-13 (c 0.138, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((3-Chlorobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19ClO[α]D20=-12 (c 0.142, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((3-Bromobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19 BrO[α]D20=-10 (c 0.168, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((4-Bromobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19 BrO[α]D20=-19 (c 0.222, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((2-Methylbenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC23H22O[α]D20=-7 (c 0.144, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((4-Methylbenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC23H22O[α]D20=-13 (c 0.244, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((3-Methoxybenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC23H22O2[α]D20=-15 (c 0.168, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((3,4-Dimethoxybenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC24H24O3[α]D20=-19 (c 0.14, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-(3-((4-Nitrobenzyl)oxy)prop-1-ene-1,3-diyl)dibenzeneC22H19NO3[α]D20=-26 (c 0.122, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-1-(((1,3-Diphenylallyl)oxy)methyl)naphthaleneC26H22O[α]D20=-17 (c 0.176, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

((R,E)-3-(Cinnamyloxy)prop-1-ene-1,3-diyl)dibenzeneC24H22O[α]D20=-19 (c 0.122, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-2-(((1,3-Diphenylallyl)oxy)methyl)furanC20H18O2[α]D20=-4 (c 0.128, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(R,E)-2-(((1,3-Diphenylallyl)oxy)methyl)thiopheneC20H18OS[α]D20=-20 (c 0.138, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(S,E)-2-(((1,3-Diphenylallyl)oxy)methyl)pyridineC21H19NO[α]D20=+14 (c 0.152, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-o-tolylphosphineAbsolute configuration: (S)

(R,E)-(3-Methoxyprop-1-ene-1,3-diyl)dibenzeneC16H16O[α]D20=+9 (c 0.164, toluene)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (R)

(S,E)-Dimethyl 2-(1,3-diphenylallyl)malonateC20H20O4[α]D20=-12 (c 0.268, CHCl3)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-p-tolylphosphineAbsolute configuration: (S)

(S,E)-N-Benzyl-1,3-diphenylprop-2-en-1-amineC22H21N[α]D20=+14 (c 0.194, CHCl3)Source of chirality: (R)-(2-(tert-butylsulfinyl)phenyl)di-o-tolylphosphineAbsolute configuration: (S)