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. Markó

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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 languageEnglish
Pages (from-to)3095-3100
Number of pages6
JournalJournal of Organic Chemistry
Volume44
Issue number18
Publication statusPublished - 1979

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phosphine
Phosphines
Phosphorus
Boiling liquids
Hydrogenation
Ligands
Derivatives
Atoms
Rhodium
Catalysts
Crystallization
cinnamic acid
arsine
tetrahydrofuran
potassium tert-butoxide

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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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.",
author = "King, {R. B.} and J. Bakos and Hoff, {C. D.} and L. Mark{\'o}",
year = "1979",
language = "English",
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journal = "Journal of Organic Chemistry",
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T1 - Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) containing terminal neomenthyl groups as ligands in asymmetric homogeneous hydrogenation catalysts

AU - King, R. B.

AU - Bakos, J.

AU - Hoff, C. D.

AU - Markó, L.

PY - 1979

Y1 - 1979

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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