Diastereoselective Synthesis of β-Substituted-α,γ-Diaminobutyric Acids and Pyrrolidines Containing Multichiral Centers

Huang, Yan; Li, Qiong; Liu, Tianliang; Xu, Peng‐Fei

doi:10.1021/jo8023076

Cited by 9 publications

(8 citation statements)

References 94 publications

(33 reference statements)

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“…Catalytic diastereoselective synthesis of these chiral building blocks mainly relies on asymmetric Michael addition reactions. Indeed, several examples of such reactions using chiral auxiliaries have been reported (Caputo et al 2006;Huang et al 2009;Yan et al 2006). However, all these reactions were performed in organic solvents.…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective Michael reaction of chiral nickel(II) glycinate with nitroalkenes for asymmetric synthesis of β-substituted α,γ-diaminobutyric acid derivatives in water

Wang

Shi

et al. 2011

Amino Acids

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We have developed the first operationally simple and environmentally benign protocol for the aqueous asymmetric Michael addition reaction of chiral nickel(II) glycinate with nitroalkenes. The reactions proceeded smoothly in the presence of TBAB (tetrabutyl ammonium bromide) in neat water at room temperature and provided good yields of β-substituted α,γ-diaminobutyric acid derivatives with excellent diastereoselectivities.

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Section: Introductionmentioning

confidence: 99%

Diastereoselective Michael reaction of chiral nickel(II) glycinate with nitroalkenes for asymmetric synthesis of β-substituted α,γ-diaminobutyric acid derivatives in water

Wang

Shi

et al. 2011

Amino Acids

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“…The presumably non-reactive imino group of these oxazinones and 15-18 only could be activated by Cu(OTf) 2 or by AgOTf as Lewis acids once the Michael adduct (for example 18) was completely formed. This second step, involving a final metal-catalyzed intramolecular Mannich-type reaction, was completed in almost quantitative yield and excellent diastereoselectivity (>99:1 dr) (Scheme 4) [33]. Both molecules endo-trans-22 and endo-cis-5a were immediately tested as chiral ligands in combination with copper(I) salts in the enantioselective catalytic 1,3-DC of imino esters 6 with various dipolarophiles (including nitroalkenes) yielding cycloadducts in very good yields and good enantioselections (see, Scheme 8) [9].…”

Section: Diastereoselective Approachesmentioning

confidence: 99%

Asymmetric 1,3-Dipolar Cycloadditons of Stabilized Azomethine Ylides with Nitroalkenes

Nejera¹,

Sansano²

2014

CTMC

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“…As excellent Michael acceptors, nitroalkenes were used to synthesize nitro-compounds and amino-compounds frequently. Therefore, we probed the Michael addition of nitroalkenes by tricycloiminolactones and expected to prepare enantiomerically enriched α,γ-diaminobutyric acids after subsequent reduction of the nitro group and removal of the auxiliary …”

Section: Synthesis Of β-Substituted αγ-Diaminobutyric Acidsmentioning

confidence: 99%

Synthesis of α-Amino Acids Based on Chiral Tricycloiminolactone Derived from Natural (+)-Camphor

et al. 2010

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Amino acids are one of the most important classes of the building blocks of life: they are the structural subunits of proteins, peptides, and many secondary metabolites. In addition to the 20 α-amino acids that constitute the backbone of proteins, hundreds of other natural α-amino acids have been discovered either in free form or as components in natural products. The difference between these molecules is the substituents at the chiral carbon situated between the amino and carboxyl moieties; this carbon (and any atom along a chain attached to it) is thus an important synthetic target. Because tailor-made α-amino acids are increasingly popular in biochemistry and organic synthesis, further refinement in synthetic methods to generate both natural (L-configuration) and unnatural (D-configuration) amino acids is a very active area of current research. In this Account, we examine the tricycloiminolactones, which are versatile glycine equivalents derived from natural camphor. We have developed the tricycloiminolactones in our laboratory and used them in the synthesis of several kinds of enantiopure α-amino acids. As nucleophiles, enolated tricycloiminolactones were shown to successfully participate in alkylations, Aldol reactions, Michael additions, and Mannich reactions. These reactions all gave excellent stereoselectivities and high yields. Simple conversion of the products offered α-alkyl-α-amino acids, α,α-dialkyl-α-amino acids, β-hydroxy-α-amino acids, α,γ-diamino acids, and α,β-diamino acids. One particular advantage is that the same electrophile can react with two chiral templates in the same way, thus affording access to both enantiomeric amino acids. In other words, some natural (L-configuration) α-amino acids and their unnatural (D-configuration) counterparts can be prepared very conveniently. The relation between substrate structures and product stereoconformations derived from our investigations serves as a convenient guide in the synthesis of useful chiral amino acids. In addition, highly stereoselective 1,3-diploar cycloadditions between alkenes and chiral nitrones derived from tricycloiminolactones provide a potential method for the synthesis of γ-hydroxy-α-amino acids. We also discuss applications of our methods in the synthesis of complex natural products, including conagenin, polyoxamic acid, lactacystin, and sphingofungin F. The preparation of some clinically important drug molecules, such as thiaphenicol, florfenicol, and chloramphenicol, was greatly simplified with our methods. The tricycloiminolactones offer a number of advantages in the synthesis of both natural and unnatural α-amino acids and provide many useful building blocks in the synthetic pursuit of complex molecules.

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Diastereoselective Synthesis of β-Substituted-α,γ-Diaminobutyric Acids and Pyrrolidines Containing Multichiral Centers

Cited by 9 publications

References 94 publications

Diastereoselective Michael reaction of chiral nickel(II) glycinate with nitroalkenes for asymmetric synthesis of β-substituted α,γ-diaminobutyric acid derivatives in water

Diastereoselective Michael reaction of chiral nickel(II) glycinate with nitroalkenes for asymmetric synthesis of β-substituted α,γ-diaminobutyric acid derivatives in water

Asymmetric 1,3-Dipolar Cycloadditons of Stabilized Azomethine Ylides with Nitroalkenes

Synthesis of α-Amino Acids Based on Chiral Tricycloiminolactone Derived from Natural (+)-Camphor

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