Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) Containing Terminal Neomenthyl Groups as Ligands in Asymmetric Homogeneous Hydrogenation Catalysts

R. B. King; J. Bakos; C. D. Hoff; L. Marko

doi:10.1021/jo01332a001

Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) Containing Terminal Neomenthyl Groups as Ligands in Asymmetric Homogeneous Hydrogenation Catalysts

R. B. King, J. Bakos, C. D. Hoff, L. Marko

Chemistry

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44 Scopus citations

Abstract

The addition of neomenthylphenylphosphine to (C₆H₅)₂PCH=CH₂ in boiling tetrahydrofuran catalyzed by potassium tert-butoxide gives the di(tertiary phosphine) (Nmen)(C₆H₅)PCH₂CH₂P(C ₆H₅)₂ (I, Nmen = neomenthyl), which could be separated by fractional crystallization into pure diastereomers differing only in the configuration at the chiral phosphorus atom. Novel features in this new di(tertiary phosphine) are the chiral terminal neomenthyl group and the nonequivalent phosphorus atoms. Asymmetric homogeneous hydrogenations of the prochiral α-(acylamido)cinnamic acid derivatives C₆H₅CH=C(NHCOR)(CO₂R′) (R = CH₃, R′ = H and CH₃; R = C₆H₅, R′ = H and C₂H₅) result in significant differences in optical yield behavior when rhodium(I) complexes of each of the two diastereomers of (Nmen)(C₆H₅)PCH₂CH₂P(C ₆H₅)₂ are used. In particular, the optical yield range for the above four prochiral α-(acylamido)cinnamic acid derivatives is 31-85% for one of the diastereomers of I but only 42-56% for the other diastereomer. The related polyphosphorus compounds C₆H₅P[CH₂CH₂P(Nmen)(C ₆H₅)]₂ and (Nmen)(C₆H₅)PCH₂CH₂P(S)(CH ₃)₂ have been obtained as mixtures of diastereomers from the additions of neomenthylphenylphosphine to C₆H₅P(CH=CH₂)₂ and CH₂=CHP(S)(CH₃)₂, respectively, in boiling tetrahydrofuran catalyzed by potassium tert-butoxide.

Original language	English (US)
Pages (from-to)	3095-3100
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	44
Issue number	18
DOIs	https://doi.org/10.1021/jo01332a001
State	Published - Feb 1 1979

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King, R. B., Bakos, J., Hoff, C. D., & Marko, L. (1979). Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) Containing Terminal Neomenthyl Groups as Ligands in Asymmetric Homogeneous Hydrogenation Catalysts. Journal of Organic Chemistry, 44(18), 3095-3100. https://doi.org/10.1021/jo01332a001

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title = "Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) Containing Terminal Neomenthyl Groups as Ligands in Asymmetric Homogeneous Hydrogenation Catalysts",

abstract = "The addition of neomenthylphenylphosphine to (C6H5)2PCH=CH2 in boiling tetrahydrofuran catalyzed by potassium tert-butoxide gives the di(tertiary phosphine) (Nmen)(C6H5)PCH2CH2P(C 6H5)2 (I, Nmen = neomenthyl), which could be separated by fractional crystallization into pure diastereomers differing only in the configuration at the chiral phosphorus atom. Novel features in this new di(tertiary phosphine) are the chiral terminal neomenthyl group and the nonequivalent phosphorus atoms. Asymmetric homogeneous hydrogenations of the prochiral α-(acylamido)cinnamic acid derivatives C6H5CH=C(NHCOR)(CO2R′) (R = CH3, R′ = H and CH3; R = C6H5, R′ = H and C2H5) result in significant differences in optical yield behavior when rhodium(I) complexes of each of the two diastereomers of (Nmen)(C6H5)PCH2CH2P(C 6H5)2 are used. In particular, the optical yield range for the above four prochiral α-(acylamido)cinnamic acid derivatives is 31-85% for one of the diastereomers of I but only 42-56% for the other diastereomer. The related polyphosphorus compounds C6H5P[CH2CH2P(Nmen)(C 6H5)]2 and (Nmen)(C6H5)PCH2CH2P(S)(CH 3)2 have been obtained as mixtures of diastereomers from the additions of neomenthylphenylphosphine to C6H5P(CH=CH2)2 and CH2=CHP(S)(CH3)2, respectively, in boiling tetrahydrofuran catalyzed by potassium tert-butoxide.",

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N2 - The addition of neomenthylphenylphosphine to (C6H5)2PCH=CH2 in boiling tetrahydrofuran catalyzed by potassium tert-butoxide gives the di(tertiary phosphine) (Nmen)(C6H5)PCH2CH2P(C 6H5)2 (I, Nmen = neomenthyl), which could be separated by fractional crystallization into pure diastereomers differing only in the configuration at the chiral phosphorus atom. Novel features in this new di(tertiary phosphine) are the chiral terminal neomenthyl group and the nonequivalent phosphorus atoms. Asymmetric homogeneous hydrogenations of the prochiral α-(acylamido)cinnamic acid derivatives C6H5CH=C(NHCOR)(CO2R′) (R = CH3, R′ = H and CH3; R = C6H5, R′ = H and C2H5) result in significant differences in optical yield behavior when rhodium(I) complexes of each of the two diastereomers of (Nmen)(C6H5)PCH2CH2P(C 6H5)2 are used. In particular, the optical yield range for the above four prochiral α-(acylamido)cinnamic acid derivatives is 31-85% for one of the diastereomers of I but only 42-56% for the other diastereomer. The related polyphosphorus compounds C6H5P[CH2CH2P(Nmen)(C 6H5)]2 and (Nmen)(C6H5)PCH2CH2P(S)(CH 3)2 have been obtained as mixtures of diastereomers from the additions of neomenthylphenylphosphine to C6H5P(CH=CH2)2 and CH2=CHP(S)(CH3)2, respectively, in boiling tetrahydrofuran catalyzed by potassium tert-butoxide.

AB - The addition of neomenthylphenylphosphine to (C6H5)2PCH=CH2 in boiling tetrahydrofuran catalyzed by potassium tert-butoxide gives the di(tertiary phosphine) (Nmen)(C6H5)PCH2CH2P(C 6H5)2 (I, Nmen = neomenthyl), which could be separated by fractional crystallization into pure diastereomers differing only in the configuration at the chiral phosphorus atom. Novel features in this new di(tertiary phosphine) are the chiral terminal neomenthyl group and the nonequivalent phosphorus atoms. Asymmetric homogeneous hydrogenations of the prochiral α-(acylamido)cinnamic acid derivatives C6H5CH=C(NHCOR)(CO2R′) (R = CH3, R′ = H and CH3; R = C6H5, R′ = H and C2H5) result in significant differences in optical yield behavior when rhodium(I) complexes of each of the two diastereomers of (Nmen)(C6H5)PCH2CH2P(C 6H5)2 are used. In particular, the optical yield range for the above four prochiral α-(acylamido)cinnamic acid derivatives is 31-85% for one of the diastereomers of I but only 42-56% for the other diastereomer. The related polyphosphorus compounds C6H5P[CH2CH2P(Nmen)(C 6H5)]2 and (Nmen)(C6H5)PCH2CH2P(S)(CH 3)2 have been obtained as mixtures of diastereomers from the additions of neomenthylphenylphosphine to C6H5P(CH=CH2)2 and CH2=CHP(S)(CH3)2, respectively, in boiling tetrahydrofuran catalyzed by potassium tert-butoxide.

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