Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination

Julian R. Moncarz, Tim J. Brunker, John C Jewett, Michael Orchowski, David S. Glueck, Roger D. Sommer, Kin Chung Lam, Christopher D. Incarvito, Thomas E. Concolino, Christopher Ceccarelli, Lev N. Zakharov, Arnold L. Rheingold

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Abstract

The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.

Original languageEnglish (US)
Pages (from-to)3205-3221
Number of pages17
JournalOrganometallics
Volume22
Issue number16
DOIs
StatePublished - Aug 4 2003
Externally publishedYes

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Stereochemistry
stereochemistry
Palladium
Catalysis
catalysis
palladium
elimination
Ligands
ligands
synthesis
X ray crystallography
Isomers
Phosphorus
configurations
Nuclear magnetic resonance
crystallography
phosphorus
Pathogen-Associated Molecular Pattern Molecules
isomers
nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination. / Moncarz, Julian R.; Brunker, Tim J.; Jewett, John C; Orchowski, Michael; Glueck, David S.; Sommer, Roger D.; Lam, Kin Chung; Incarvito, Christopher D.; Concolino, Thomas E.; Ceccarelli, Christopher; Zakharov, Lev N.; Rheingold, Arnold L.

In: Organometallics, Vol. 22, No. 16, 04.08.2003, p. 3205-3221.

Research output: Contribution to journalArticle

Moncarz, JR, Brunker, TJ, Jewett, JC, Orchowski, M, Glueck, DS, Sommer, RD, Lam, KC, Incarvito, CD, Concolino, TE, Ceccarelli, C, Zakharov, LN & Rheingold, AL 2003, 'Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination', Organometallics, vol. 22, no. 16, pp. 3205-3221. https://doi.org/10.1021/om030144x
Moncarz, Julian R. ; Brunker, Tim J. ; Jewett, John C ; Orchowski, Michael ; Glueck, David S. ; Sommer, Roger D. ; Lam, Kin Chung ; Incarvito, Christopher D. ; Concolino, Thomas E. ; Ceccarelli, Christopher ; Zakharov, Lev N. ; Rheingold, Arnold L. / Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination. In: Organometallics. 2003 ; Vol. 22, No. 16. pp. 3205-3221.
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abstract = "The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.",
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T1 - Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination

AU - Moncarz, Julian R.

AU - Brunker, Tim J.

AU - Jewett, John C

AU - Orchowski, Michael

AU - Glueck, David S.

AU - Sommer, Roger D.

AU - Lam, Kin Chung

AU - Incarvito, Christopher D.

AU - Concolino, Thomas E.

AU - Ceccarelli, Christopher

AU - Zakharov, Lev N.

AU - Rheingold, Arnold L.

PY - 2003/8/4

Y1 - 2003/8/4

N2 - The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.

AB - The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.

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