Microbiological and chemical methods in the asymmetric oxidation of sulfides: A comparative study for the preparation of (S)-vinyl sulfoxides

Rossi, C.; Fauve, A.; Madesclaire, M.; Roche, D.; Davis, Franklin A.; Reddy, R. T.

doi:10.1016/s0957-4166(00)82296-x

Cited by 33 publications

(8 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides, E ‐ or Z ‐vinyl sulfoxides can be achieved via the stereoselective reduction of alkynyl sulfoxides [4b] . In addition, chiral vinyl sulfoxides are prepared by asymmetric oxidation of vinyl thioether [5a] . α‐substituted vinyl sulfoxides are made from α‐halo vinyl sulfoxides and aryl/alkenyl boronic acids through Suzuki coupling (Scheme 1a) [5b] …”

Section: Introductionmentioning

confidence: 99%

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

et al. 2021

View full text Add to dashboard Cite

Methods to synthesize α‐substituted alkenyl sulfoxides are highly useful as they are widely used to construct diverse molecules of high synthetic importance. We have described a synthetic route for expedient access to the numerous α‐substituted alkenyl sulfoxides from alkynes and β‐sulfinyl esters. This protocol exhibits a vast substrate scope, readily accommodates a wide range of functional groups, and is scalable in a gram‐scale. Besides, we demonstrated a direct synthesis of alkenyl sulfoxides from thiols via the in situ generation of the requisite β‐sulfinyl ester. The ensuing α‐substituted alkenyl sulfoxide product was readily transformed into benzofuran and sulfonyl derivatives. Mechanistic investigations were done to comprehend the reaction mechanism.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

et al. 2021

View full text Add to dashboard Cite

show abstract

“…The most practical process to make chiral sulfoxides from sulfides is the Kagan oxidation catalyzed by titanium(IV) isopropoxide and chiral diol ligands. A survey of the literature indicated that reaction conditions have to be carefully optimized for each substrate (18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30). Our preliminary screening of ligands under the original Kagan conditions (20,21) revealed that diisopropyl tartrate gave an ee of 38% and diethyl tartrate gave slightly lower ee.…”

Section: Preparation Of Benzoxathiin 6 Preparation Of This Key Intermentioning

confidence: 99%

An efficient asymmetric synthesis of an estrogen receptor modulator by sulfoxide-directed borane reduction

Song

King²,

Waters³

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

An efficient asymmetric synthesis of a selective estrogen receptor modulator (SERM) that has a dihydrobenzoxathiin core structure bearing two stereogenic centers is reported. The stereogenic centers were established by an unprecedented chiral sulfoxide-directed stereospecific reduction of an ␣,␤-unsaturated sulfoxide to the saturated sulfide in one step. Studies to elucidate the mechanism for this reduction are reported. Highly efficient Cu(I)-mediated ether formation was used to install the ether side chain, and selective debenzylation conditions were developed to remove the benzyl protecting groups on the phenols. E strogen receptors (ERs) are members of the steroid hormone nuclear receptor superfamily. They are ligand-dependent transcription factors that bind to specific DNA sequences and regulate gene expression. There are two known members of the estrogen receptor family, ER␣ and ER␤, encoded by distinct genes. ER modulators are potentially useful agents for treatment or prevention of a variety of conditions related to estrogen functions, including bone loss, cartilage degeneration, endometriosis, uterine fibroid disease, hot flashes, increased levels of low-density lipoprotein cholesterol, cardiovascular disease, obesity, incontinence, and cancer (refs. 1-4 and references cited in ref. 4). SERMs are ER ligands that act like estrogens in some tissues, but block estrogen action in others. Thus, SERMs may exhibit an agonistic or antagonistic activity, depending on the context in which their activity is examined. Fig. 1) is a potent ER␣ SERM being evaluated as part of the selective ER antagonist program at Merck (1-4). Although there are several methods for the synthesis of the core cis-2,3-disubstituted-dihydrobenzoxathiin, the asymmetric synthesis of these compounds has not been reported (1-7). Herein, we report an enantioselective synthesis of 1. Experimental ProceduresGeneral. Chemicals were used as received from commercial sources unless otherwise noted. NMR data were collected on Bruker Avance NMR spectrometers. Chemical shifts are reported in ppm downfield from tetramethylsilane. HPLC purity data are reported as area percentage of the desired peak from the total peaks. HPLC conditions are listed in supporting information, which is published on the PNAS web site. High-resolution mass spectrometer (HRMS) data were collected on a Micromass API US Ultima quadrupole time-of-flight (QTOF) mass spectrometer. Vinyl Sulfide 6.A 100-liter round-bottom flask was charged with ketone 7 (8.01 kg, 12.2 mol) and 48 liters of acetonitrile followed by phenylphosphonic dichloride (2.50 kg, 12.9 mol). The flask was fitted with a reflux condenser with off-gases vented through a caustic scrubber, and the reaction mixture was heated to reflux (75°C). After about 2 h, HPLC assay showed Ͼ99% conversion. The reaction mixture was concentrated under reduced pressure at 20-50°C to 28 liters. Diisopropylethylamine (786 g, 6.08 mol) was added, followed by 28 liters of denatured ethanol (denatured with 0.5% toluene). The solution was ...

show abstract

“…Although a number of chemical methods for the production of optically active sulfoxides have been investigated (Solladie, 1981; Carreno, 1995) biological approaches have also been applied. For example, racemic sulfoxides containing an ester group have been resolved using ester hydrolase (Burgess et al, 1992) and prochiral sulfides have been asymmetrically oxidized by both whole cells (Rossi et al, 1992; Holland, 1988; Holland et al, 1995) and isolated enzymes (Colonna et al, 1990).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric reduction of racemic sulfoxides by dimethyl sulfoxide reductases from Rhodobacter capsulatus, Escherichia coli and Proteus species

Hanlon

Graham²,

Hogan

et al. 1998

Microbiology

View full text Add to dashboard Cite

The enantioselective reduction of racemic sulfoxides by dimethyl sulfoxide reductases from Rhodobacter capsulatus, Escherichia coli, Proteus mirabilis and Proteus vulgaris was investigated. Purified dimethyl sulfoxide reductase from Rhodobacter capsulatus catalysed the selective removal of (S)-methyl p-tolyl sulfoxide from a racemic mixture of methyl p-tolyl sulfoxide and resulted in an 88 O/ o recovery of enantiomerically pure (R)-methyl pltolyl sulfoxide. Rhodobacter capsulatus was shown to be able to grow photoheterotrophically in the presence of certain chiral sulfoxides under conditions where a sulfoxide is needed as an electron sink. Whole cells of Rhodobacter capsulatus were shown to catalyse the enantioselective reduction of methyl p-tolyl sulfoxide, ethyl 2-pyridyl sulfoxide, methylthiomethyl methyl sulfoxide and methoxymethyl phenyl sulfoxide. Similarly, whole cells of Escherichia coli, Proteus mirabilis and Proteus vulgaris reduced these sulfoxides but with opposite enantioselectivity.

show abstract

Microbiological and chemical methods in the asymmetric oxidation of sulfides: A comparative study for the preparation of (S)-vinyl sulfoxides

Cited by 33 publications

References 36 publications

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

An efficient asymmetric synthesis of an estrogen receptor modulator by sulfoxide-directed borane reduction

Asymmetric reduction of racemic sulfoxides by dimethyl sulfoxide reductases from Rhodobacter capsulatus, Escherichia coli and Proteus species

Contact Info

Product

Resources

About