Chiral phosphinooxazoline-ruthenium(II) and -osmium(II) complexes as catalysts in Diels-Alder reactions

Daniel Carmona; Cristina Vega; Néstor García; Fernando J. Lahoz; Sergio Elipe; Luis A. Oro; M. Pilar Lamata; Fernando Viguri; Rosana Borao

doi:10.1021/om050973d

Chiral phosphinooxazoline-ruthenium(II) and -osmium(II) complexes as catalysts in Diels-Alder reactions

Daniel Carmona^*
, Cristina Vega
, Néstor García
, Fernando J. Lahoz
, Sergio Elipe
, Luis A. Oro
, M. Pilar Lamata
, Fernando Viguri
, Rosana Borao

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

47 Scopus citations

Abstract

The synthesis and characterization of optically active phosphinooxazoline chloride complexes (S_M and R_M)-[(η⁶-p- MeC₆H₄iPr)MCl(PN)]A (M = Ru, Os; PN = phosphinooxazoline ligand; A = counteranion) and the derived aqua complexes (R_M and S_M)-[(η⁶-p-MeC₆H₄iPr)M(PN) (H₂O)](A)₂ are reported. The OPOF₂-containing compounds (R_M and S_M)-[(η⁶-p-MeC ₆H₄iPr)M(OPOF₂)(PNiPr)][PF₆] (M = Ru, Os; PNiPr = (4S)-2-(2-diphenylphosphinophenyl)-4-isopropyl-1,3-oxazoline) have been also prepared and characterized. The molecular structures of (S _M)-[(η⁶-p-MeC₆H₄iPr)MCl(PNiPr)] [SbF₆] (M = Ru, Os), (S_Ru)-[(η⁶-p-MeC ₆H₄iPr)RuCl(PNInd)][SbF₆] (PNInd = (3aS,8aR)-2-(2-diphenylphosphinophenyl)-3a,-8a-dihydroindane [1,2-d]oxazole), and (R_Ru)-[(η⁶-p-MeC₆H₄iPr) Ru(PNiPr)(H₂O)][SbF₆] and that of the OPOF ₂-containing compounds (R_Ru and S_Ru)- [(η⁶-p-MeC₆H₄iPr)Ru(OPOF ₂)(PNiPr)][PF₆] have been determined by X-ray diffractometric methods. Dichloromethane solutions of the aqua complexes [(η⁶-p-MeC₆H₄iPr)M(PN)(H ₂O)][SbF₆]₂ are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. The reaction occurs rapidly at room temperature with good exo:endo selectivity (from 85:15 to 96:4) and moderate enantioselectivity (up to 47%). The intermediate Lewis acid-dienophile compound (R_Ru and S_Ru)- [(η⁶-p-MeC₆H₄iPr)Ru(PNInd)(methacrolein)] [SbF₆]₂ was isolated, and the molecular structure of the S epimer was determined by diffractometric means. The osmium complexes (S _Os and R_Os)- [(η⁶-p-MeC₆H ₄iPr)Os(PN)(H₂O)][A]₂ (PN = PNiPr, A = SbF ₆, BF₄; PN = PNInd, A = SbF₆) evolve to the phenyl-containing compounds (S_Os and R_Os)- [(η⁶-p-MeC₆H₄iPr)OsPh(PN′)][SbF ₆] (PN′ = (4S)-2-(2-hydroxyphenylphosphinophenyl)-4-isopropyl- 1,3-oxazoline (PNOHiPr), PN′ = (3aS,8aR)-2-(2- hydroxyphenylphosphinophenyl)-3a,8a-dihydroindane[1,2d]oxazole] (PNOHInd)) and (S_Os and R_Os)-[(η⁶-p-MeC₆H ₄iPr)OsPh(PNFiPr)][BF₄] (PNFiPr = (4S)-2-(2- fluorophenylphosphinophenyl)-4-isopropyl-1,3-oxazoline), respectively, in which the phosphinooxazoline ligand incorporates a hydroxy or fluoro functionality. On the basis of spectroscopic and crystallographic observations, a common pathway for these reactions is proposed.

Original language	English
Pages (from-to)	1592-1606
Number of pages	15
Journal	Organometallics
Volume	25
Issue number	7
DOIs	https://doi.org/10.1021/om050973d
State	Published - 27 Mar 2006
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om050973d

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@article{bd08c7b62102423bb197236f884ca91a,

title = "Chiral phosphinooxazoline-ruthenium(II) and -osmium(II) complexes as catalysts in Diels-Alder reactions",

abstract = "The synthesis and characterization of optically active phosphinooxazoline chloride complexes (SM and RM)-[(η6-p- MeC6H4iPr)MCl(PN)]A (M = Ru, Os; PN = phosphinooxazoline ligand; A = counteranion) and the derived aqua complexes (RM and SM)-[(η6-p-MeC6H4iPr)M(PN) (H2O)](A)2 are reported. The OPOF2-containing compounds (RM and SM)-[(η6-p-MeC 6H4iPr)M(OPOF2)(PNiPr)][PF6] (M = Ru, Os; PNiPr = (4S)-2-(2-diphenylphosphinophenyl)-4-isopropyl-1,3-oxazoline) have been also prepared and characterized. The molecular structures of (S M)-[(η6-p-MeC6H4iPr)MCl(PNiPr)] [SbF6] (M = Ru, Os), (SRu)-[(η6-p-MeC 6H4iPr)RuCl(PNInd)][SbF6] (PNInd = (3aS,8aR)-2-(2-diphenylphosphinophenyl)-3a,-8a-dihydroindane [1,2-d]oxazole), and (RRu)-[(η6-p-MeC6H4iPr) Ru(PNiPr)(H2O)][SbF6] and that of the OPOF 2-containing compounds (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(OPOF 2)(PNiPr)][PF6] have been determined by X-ray diffractometric methods. Dichloromethane solutions of the aqua complexes [(η6-p-MeC6H4iPr)M(PN)(H 2O)][SbF6]2 are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. The reaction occurs rapidly at room temperature with good exo:endo selectivity (from 85:15 to 96:4) and moderate enantioselectivity (up to 47\%). The intermediate Lewis acid-dienophile compound (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(PNInd)(methacrolein)] [SbF6]2 was isolated, and the molecular structure of the S epimer was determined by diffractometric means. The osmium complexes (S Os and ROs)- [(η6-p-MeC6H 4iPr)Os(PN)(H2O)][A]2 (PN = PNiPr, A = SbF 6, BF4; PN = PNInd, A = SbF6) evolve to the phenyl-containing compounds (SOs and ROs)- [(η6-p-MeC6H4iPr)OsPh(PN′)][SbF 6] (PN′ = (4S)-2-(2-hydroxyphenylphosphinophenyl)-4-isopropyl- 1,3-oxazoline (PNOHiPr), PN′ = (3aS,8aR)-2-(2- hydroxyphenylphosphinophenyl)-3a,8a-dihydroindane[1,2d]oxazole] (PNOHInd)) and (SOs and ROs)-[(η6-p-MeC6H 4iPr)OsPh(PNFiPr)][BF4] (PNFiPr = (4S)-2-(2- fluorophenylphosphinophenyl)-4-isopropyl-1,3-oxazoline), respectively, in which the phosphinooxazoline ligand incorporates a hydroxy or fluoro functionality. On the basis of spectroscopic and crystallographic observations, a common pathway for these reactions is proposed.",

author = "Daniel Carmona and Cristina Vega and N{\'e}stor Garc{\'i}a and Lahoz, \{Fernando J.\} and Sergio Elipe and Oro, \{Luis A.\} and Lamata, \{M. Pilar\} and Fernando Viguri and Rosana Borao",

year = "2006",

month = mar,

day = "27",

doi = "10.1021/om050973d",

language = "English",

volume = "25",

pages = "1592--1606",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Chiral phosphinooxazoline-ruthenium(II) and -osmium(II) complexes as catalysts in Diels-Alder reactions

AU - Carmona, Daniel

AU - Vega, Cristina

AU - García, Néstor

AU - Lahoz, Fernando J.

AU - Elipe, Sergio

AU - Oro, Luis A.

AU - Lamata, M. Pilar

AU - Viguri, Fernando

AU - Borao, Rosana

PY - 2006/3/27

Y1 - 2006/3/27

N2 - The synthesis and characterization of optically active phosphinooxazoline chloride complexes (SM and RM)-[(η6-p- MeC6H4iPr)MCl(PN)]A (M = Ru, Os; PN = phosphinooxazoline ligand; A = counteranion) and the derived aqua complexes (RM and SM)-[(η6-p-MeC6H4iPr)M(PN) (H2O)](A)2 are reported. The OPOF2-containing compounds (RM and SM)-[(η6-p-MeC 6H4iPr)M(OPOF2)(PNiPr)][PF6] (M = Ru, Os; PNiPr = (4S)-2-(2-diphenylphosphinophenyl)-4-isopropyl-1,3-oxazoline) have been also prepared and characterized. The molecular structures of (S M)-[(η6-p-MeC6H4iPr)MCl(PNiPr)] [SbF6] (M = Ru, Os), (SRu)-[(η6-p-MeC 6H4iPr)RuCl(PNInd)][SbF6] (PNInd = (3aS,8aR)-2-(2-diphenylphosphinophenyl)-3a,-8a-dihydroindane [1,2-d]oxazole), and (RRu)-[(η6-p-MeC6H4iPr) Ru(PNiPr)(H2O)][SbF6] and that of the OPOF 2-containing compounds (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(OPOF 2)(PNiPr)][PF6] have been determined by X-ray diffractometric methods. Dichloromethane solutions of the aqua complexes [(η6-p-MeC6H4iPr)M(PN)(H 2O)][SbF6]2 are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. The reaction occurs rapidly at room temperature with good exo:endo selectivity (from 85:15 to 96:4) and moderate enantioselectivity (up to 47%). The intermediate Lewis acid-dienophile compound (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(PNInd)(methacrolein)] [SbF6]2 was isolated, and the molecular structure of the S epimer was determined by diffractometric means. The osmium complexes (S Os and ROs)- [(η6-p-MeC6H 4iPr)Os(PN)(H2O)][A]2 (PN = PNiPr, A = SbF 6, BF4; PN = PNInd, A = SbF6) evolve to the phenyl-containing compounds (SOs and ROs)- [(η6-p-MeC6H4iPr)OsPh(PN′)][SbF 6] (PN′ = (4S)-2-(2-hydroxyphenylphosphinophenyl)-4-isopropyl- 1,3-oxazoline (PNOHiPr), PN′ = (3aS,8aR)-2-(2- hydroxyphenylphosphinophenyl)-3a,8a-dihydroindane[1,2d]oxazole] (PNOHInd)) and (SOs and ROs)-[(η6-p-MeC6H 4iPr)OsPh(PNFiPr)][BF4] (PNFiPr = (4S)-2-(2- fluorophenylphosphinophenyl)-4-isopropyl-1,3-oxazoline), respectively, in which the phosphinooxazoline ligand incorporates a hydroxy or fluoro functionality. On the basis of spectroscopic and crystallographic observations, a common pathway for these reactions is proposed.

AB - The synthesis and characterization of optically active phosphinooxazoline chloride complexes (SM and RM)-[(η6-p- MeC6H4iPr)MCl(PN)]A (M = Ru, Os; PN = phosphinooxazoline ligand; A = counteranion) and the derived aqua complexes (RM and SM)-[(η6-p-MeC6H4iPr)M(PN) (H2O)](A)2 are reported. The OPOF2-containing compounds (RM and SM)-[(η6-p-MeC 6H4iPr)M(OPOF2)(PNiPr)][PF6] (M = Ru, Os; PNiPr = (4S)-2-(2-diphenylphosphinophenyl)-4-isopropyl-1,3-oxazoline) have been also prepared and characterized. The molecular structures of (S M)-[(η6-p-MeC6H4iPr)MCl(PNiPr)] [SbF6] (M = Ru, Os), (SRu)-[(η6-p-MeC 6H4iPr)RuCl(PNInd)][SbF6] (PNInd = (3aS,8aR)-2-(2-diphenylphosphinophenyl)-3a,-8a-dihydroindane [1,2-d]oxazole), and (RRu)-[(η6-p-MeC6H4iPr) Ru(PNiPr)(H2O)][SbF6] and that of the OPOF 2-containing compounds (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(OPOF 2)(PNiPr)][PF6] have been determined by X-ray diffractometric methods. Dichloromethane solutions of the aqua complexes [(η6-p-MeC6H4iPr)M(PN)(H 2O)][SbF6]2 are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. The reaction occurs rapidly at room temperature with good exo:endo selectivity (from 85:15 to 96:4) and moderate enantioselectivity (up to 47%). The intermediate Lewis acid-dienophile compound (RRu and SRu)- [(η6-p-MeC6H4iPr)Ru(PNInd)(methacrolein)] [SbF6]2 was isolated, and the molecular structure of the S epimer was determined by diffractometric means. The osmium complexes (S Os and ROs)- [(η6-p-MeC6H 4iPr)Os(PN)(H2O)][A]2 (PN = PNiPr, A = SbF 6, BF4; PN = PNInd, A = SbF6) evolve to the phenyl-containing compounds (SOs and ROs)- [(η6-p-MeC6H4iPr)OsPh(PN′)][SbF 6] (PN′ = (4S)-2-(2-hydroxyphenylphosphinophenyl)-4-isopropyl- 1,3-oxazoline (PNOHiPr), PN′ = (3aS,8aR)-2-(2- hydroxyphenylphosphinophenyl)-3a,8a-dihydroindane[1,2d]oxazole] (PNOHInd)) and (SOs and ROs)-[(η6-p-MeC6H 4iPr)OsPh(PNFiPr)][BF4] (PNFiPr = (4S)-2-(2- fluorophenylphosphinophenyl)-4-isopropyl-1,3-oxazoline), respectively, in which the phosphinooxazoline ligand incorporates a hydroxy or fluoro functionality. On the basis of spectroscopic and crystallographic observations, a common pathway for these reactions is proposed.

UR - https://www.scopus.com/pages/publications/33645867975

U2 - 10.1021/om050973d

DO - 10.1021/om050973d

M3 - Article

AN - SCOPUS:33645867975

SN - 0276-7333

VL - 25

SP - 1592

EP - 1606

JO - Organometallics

JF - Organometallics

IS - 7

ER -

Chiral phosphinooxazoline-ruthenium(II) and -osmium(II) complexes as catalysts in Diels-Alder reactions

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