Enantioselective Synthesis of Both Enantiomers of Methyl Dihydrojasmonate Using Solid−Liquid Asymmetric Phase-Transfer Catalysis

Perrard, Thierry; Plaquevent, Jean‐Christophe; Desmurs, Jean‐Roger; Hébrault, Dominique

doi:10.1021/ol006207e

Cited by 98 publications

(35 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[16,21] As shown in Table 1, the epoxidation of 7 could be achieved in good yields using either hydrogen peroxide, tert-butyl hydroperoxide (TBHP), cumyl Scheme 1. Asymmetric epoxidation of chalcone derivatives using phasetransfer catalysts.…”

Section: Resultsmentioning

confidence: 99%

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Berkessel

Guixà

Schmidt

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

In the area of catalytic asymmetric epoxidation, the highly enantioselective transformation of cyclic enones and quinones is an extremely challenging target. With the aim to develop new and highly effective phase-transfer catalysts for this purpose, we conducted a systematic structural variation of PTCs based on quinine and quinidine. In the total of 15 new quaternary ammonium PTCs, modifications included, for example, the exchange of the quinine methoxy group for a free hydroxyl or other alkoxy substituents, and the introduction of additional elements of chirality through alkylation of the alkaloid quinuclidine nitrogen atom by chiral electrophiles. For example, the well-established 9- anthracenylmethyl group was exchanged for a "chiral" anthracene in the form of 9-chloromethyl-[(1,8-S;4,5-R)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene. The asymmetric epoxidation of vitamin K(3) was used as the test reaction for our novel PTCs. The readily available PTC 10 (derived from quinine in three convenient and high-yielding steps) proved to be the most enantioselective catalyst for this purpose known to date: At a catalyst loading of only 2.50 mol %, the quinone epoxide was obtained in 76 % yield and with 85 % ee (previously: < or =34 % ee), using commercial bleach (aqueous sodium hypochlorite) as the oxidant. To rationalize the sense of induction effected by our novel phase-transfer catalysts, a computational analysis of steric interactions in the intermediate chlorooxy enolate-PTC ion pair was conducted. Based on this analysis, the sense of induction for all 15 novel PTCs could be consistently explained.

show abstract

Section: Resultsmentioning

confidence: 99%

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Berkessel

Guixà

Schmidt

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…For example, the reaction was investigated in the presence of La-BINOL complexes, 53,54 L-proline derivatives, 55 chiral aminoalcohol-Al complexes, 56,57 pyrrolidylalkyl ammonium hydroxide, and chiral ammonium salts 58 as the catalysts. There are also a few examples in this field for chiral phase transfer catalysis.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of l‐threitol‐based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions

et al. 2017

View full text Add to dashboard Cite

A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers.

show abstract

“…The addition of diester 178 to cyclic enone was applied by Plaquevent et al in the synthesis of methyl dihydrojasmonate, a natural ketone with olfactory properties isolated from Jasminum grandiforum L (Scheme 11.43). 77 Despite the relatively moderate 80% ee and large excess of dimethyl malonate required (30 equiv), the rapidity of the synthesis (two steps to the natural product) and the simple reaction conditions remained attractive for scaleup.…”

Section: Synthesis Of 175mentioning

confidence: 99%

Organocatalytic Conjugate Addition in Stereoselective Synthesis

Quintard

Alexakis

2013

Stereoselective Synthesis of Drugs and Natural Products

View full text Add to dashboard Cite

Conjugate addition is a privileged method in organic synthesis allowing for the formation of new CC bonds, molecules that can serve as valuable synthons for total synthesis. It is highly attractive thanks to the presence of at least one functional group on the Michael partners, a group that can be easily derivatized. In this field, organocatalyzed reactions have recently changed the way of thinking about synthetic approaches, notably, as soon as carbonyl groups are involved. As a result, numerous applications of organocatalytic Michael additions in natural product synthesis have emerged in the last few years.

show abstract

Enantioselective Synthesis of Both Enantiomers of Methyl Dihydrojasmonate Using Solid−Liquid Asymmetric Phase-Transfer Catalysis

Cited by 98 publications

References 12 publications

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Synthesis of l‐threitol‐based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions

Organocatalytic Conjugate Addition in Stereoselective Synthesis

Contact Info

Product

Resources

About

Enantioselective Synthesis of Both Enantiomers of Methyl Dihydrojasmonate Using Solid−Liquid Asymmetric Phase-Transfer Catalysis

Cited by 98 publications

References 12 publications

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K3) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K3) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Synthesis of l‐threitol‐based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions

Organocatalytic Conjugate Addition in Stereoselective Synthesis

Contact Info

Product

Resources

About

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts

Highly Enantioselective Epoxidation of 2‐Methylnaphthoquinone (Vitamin K₃) Mediated by New Cinchona Alkaloid Phase‐Transfer Catalysts