Stereoretentive formylation of (S)-proline: new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ)

Mehmet Temizsoy; Waqas Sethi; Anders Reinholdt; Magnus Schau-Magnussen; Jesper Bendix; Anders Hammershøi

doi:10.1039/c5dt02674a

Stereoretentive formylation of (S)-proline: new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ)

Mehmet Temizsoy, Waqas Sethi, Anders Reinholdt, Magnus Schau-Magnussen, Jesper Bendix, Anders Hammershøi

Department of Chemistry

2 Citations (Scopus)

Abstract

In a Vilsmeier-Haack-type formylation reaction the α-(dihydroxymethyl)-(S)-prolinato complex (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22) was produced stereoselectively (85% ee) from the (S)-prolinato complex, (+)578-p-[Co(tren){(SC,SN)-ProO}]2(H3O)2(HOEt2)(O3SCF3)7 (18). Similar reaction of the (S)-alaninato complex, (-)578-p-[Co(tren)(S-AlaO)](H3O)(O3SCF3)3 (13), produced the racemate, rac-p-[Co(tren)(Ala{CH(OH)2}O)]SO4·2H2O (17). The contrasting stereochemical outcomes of the formylation reaction with 18versus13 were ascribed to the stereogenic character of the coordinated sec. amine of the (S)-prolinate chelate in 18, which serves to uphold a chiral environment during reaction, whereas reaction intermediates derived from 13 lack this stereochemical feature. The stereoselective formylation of (S)-proline, relying on coordination to an inert metal centre, as conducted here, constitutes a novel application of the concept of Self-Regeneration of Stereocentres (SRS). The α-(hydroxymethyl)-(S)-prolinato complex, (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) resulted from borohydride reduction of 22. The molecular structures of (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22), rac-p-[Co(tren)-(Ala{CH(OH)2}O)]I2·H2O (17) and (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) were established by X-ray crystallography.

Original language	English
Journal	Dalton Transactions (Print Edition)
Volume	44
Issue number	42
Pages (from-to)	18438-18446
Number of pages	9
ISSN	1477-9226
DOIs	https://doi.org/10.1039/c5dt02674a
Publication status	Published - 2015

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Stereoretentive formylation of (S)-proline: new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ) . / Temizsoy, Mehmet; Sethi, Waqas; Reinholdt, Anders et al.
In: Dalton Transactions (Print Edition), Vol. 44, No. 42, 2015, p. 18438-18446.

Research output: Contribution to journal › Journal article › Research › peer-review

@article{47db086c29154dec8d7b35599bff529a,

title = "Stereoretentive formylation of (S)-proline: new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ) ",

abstract = "In a Vilsmeier-Haack-type formylation reaction the α-(dihydroxymethyl)-(S)-prolinato complex (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22) was produced stereoselectively (85% ee) from the (S)-prolinato complex, (+)578-p-[Co(tren){(SC,SN)-ProO}]2(H3O)2(HOEt2)(O3SCF3)7 (18). Similar reaction of the (S)-alaninato complex, (-)578-p-[Co(tren)(S-AlaO)](H3O)(O3SCF3)3 (13), produced the racemate, rac-p-[Co(tren)(Ala{CH(OH)2}O)]SO4·2H2O (17). The contrasting stereochemical outcomes of the formylation reaction with 18versus13 were ascribed to the stereogenic character of the coordinated sec. amine of the (S)-prolinate chelate in 18, which serves to uphold a chiral environment during reaction, whereas reaction intermediates derived from 13 lack this stereochemical feature. The stereoselective formylation of (S)-proline, relying on coordination to an inert metal centre, as conducted here, constitutes a novel application of the concept of Self-Regeneration of Stereocentres (SRS). The α-(hydroxymethyl)-(S)-prolinato complex, (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) resulted from borohydride reduction of 22. The molecular structures of (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22), rac-p-[Co(tren)-(Ala{CH(OH)2}O)]I2·H2O (17) and (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) were established by X-ray crystallography.",

author = "Mehmet Temizsoy and Waqas Sethi and Anders Reinholdt and Magnus Schau-Magnussen and Jesper Bendix and Anders Hammersh{\o}i",

year = "2015",

doi = "10.1039/c5dt02674a",

language = "English",

volume = "44",

pages = "18438--18446",

journal = "Dalton Transactions (Print Edition)",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "42",

}

TY - JOUR

T1 - Stereoretentive formylation of (S)-proline

T2 - new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ)

AU - Temizsoy, Mehmet

AU - Sethi, Waqas

AU - Reinholdt, Anders

AU - Schau-Magnussen, Magnus

AU - Bendix, Jesper

AU - Hammershøi, Anders

PY - 2015

Y1 - 2015

N2 - In a Vilsmeier-Haack-type formylation reaction the α-(dihydroxymethyl)-(S)-prolinato complex (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22) was produced stereoselectively (85% ee) from the (S)-prolinato complex, (+)578-p-[Co(tren){(SC,SN)-ProO}]2(H3O)2(HOEt2)(O3SCF3)7 (18). Similar reaction of the (S)-alaninato complex, (-)578-p-[Co(tren)(S-AlaO)](H3O)(O3SCF3)3 (13), produced the racemate, rac-p-[Co(tren)(Ala{CH(OH)2}O)]SO4·2H2O (17). The contrasting stereochemical outcomes of the formylation reaction with 18versus13 were ascribed to the stereogenic character of the coordinated sec. amine of the (S)-prolinate chelate in 18, which serves to uphold a chiral environment during reaction, whereas reaction intermediates derived from 13 lack this stereochemical feature. The stereoselective formylation of (S)-proline, relying on coordination to an inert metal centre, as conducted here, constitutes a novel application of the concept of Self-Regeneration of Stereocentres (SRS). The α-(hydroxymethyl)-(S)-prolinato complex, (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) resulted from borohydride reduction of 22. The molecular structures of (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22), rac-p-[Co(tren)-(Ala{CH(OH)2}O)]I2·H2O (17) and (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) were established by X-ray crystallography.

AB - In a Vilsmeier-Haack-type formylation reaction the α-(dihydroxymethyl)-(S)-prolinato complex (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22) was produced stereoselectively (85% ee) from the (S)-prolinato complex, (+)578-p-[Co(tren){(SC,SN)-ProO}]2(H3O)2(HOEt2)(O3SCF3)7 (18). Similar reaction of the (S)-alaninato complex, (-)578-p-[Co(tren)(S-AlaO)](H3O)(O3SCF3)3 (13), produced the racemate, rac-p-[Co(tren)(Ala{CH(OH)2}O)]SO4·2H2O (17). The contrasting stereochemical outcomes of the formylation reaction with 18versus13 were ascribed to the stereogenic character of the coordinated sec. amine of the (S)-prolinate chelate in 18, which serves to uphold a chiral environment during reaction, whereas reaction intermediates derived from 13 lack this stereochemical feature. The stereoselective formylation of (S)-proline, relying on coordination to an inert metal centre, as conducted here, constitutes a novel application of the concept of Self-Regeneration of Stereocentres (SRS). The α-(hydroxymethyl)-(S)-prolinato complex, (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) resulted from borohydride reduction of 22. The molecular structures of (+)578-p-[Co(tren){(RC,SN)-Pro[CH(OH)2]O}]Cl2·2H2O (22), rac-p-[Co(tren)-(Ala{CH(OH)2}O)]I2·H2O (17) and (+)578-p-[Co(tren){(RC,SN)-Pro(CH2OH)O}]Cl2·2H2O (23) were established by X-ray crystallography.

U2 - 10.1039/c5dt02674a

DO - 10.1039/c5dt02674a

M3 - Journal article

C2 - 26440587

SN - 1477-9226

VL - 44

SP - 18438

EP - 18446

JO - Dalton Transactions (Print Edition)

JF - Dalton Transactions (Print Edition)

IS - 42

ER -

Stereoretentive formylation of (S)-proline: new application of the self-regeneration of stereo-centres (SRS) principle via chelation to cobalt(ɪɪɪ)

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