Solid-phase total synthesis and structural confirmation of antimicrobial longicatenamide A

• Takumi Matsumoto,
• Takefumi Kuranaga,
• Yuto Taniguchi,
• Weicheng Wang and
• Hideaki Kakeya

Beilstein J. Org. Chem. 2022, 18, 1560–1566, doi:10.3762/bjoc.18.166

• unavailable building blocks 7 and 10 were chemically constructed from readily available starting materials. The synthesis of building block 10 commenced with the synthesis of compound 15 through Wittig reaction of Garner’s aldehyde (13) [16], which was readily obtained from tert-butyloxycarbonyl (Boc

N-(1-Phenylethyl)aziridine-2-carboxylate esters in the synthesis of biologically relevant compounds

• Iwona E. Głowacka,
• Aleksandra Trocha,
• Andrzej E. Wróblewski and
• Dorota G. Piotrowska

Beilstein J. Org. Chem. 2019, 15, 1722–1757, doi:10.3762/bjoc.15.168

• Iwona E. Glowacka Aleksandra Trocha Andrzej E. Wroblewski Dorota G. Piotrowska Bioorganic Chemistry Laboratory, Faculty of Pharmacy, Medical University of Lodz, Muszynskiego 1, 90-151 Lodz, Poland 10.3762/bjoc.15.168 Abstract Since Garner’s aldehyde has several drawbacks, first of all is prone to

• could be prepared from ᴅ-mannitol. While derivatives of glyceraldehyde are configurationally stable Garner’s aldehyde 3a [8][9], available from ʟ-serine, is configurationally labile and samples with ee as low as 75% can be obtained depending on the reaction conditions. Significant improvement in terms

• which is finally easily removed [11]. Among three-carbon chirons related to Garner’s aldehyde derivatives of N-(1-phenylethyl)aziridine-2-carboxylic acid 5–8 (Figure 2) play an important role in asymmetric synthesis as they function as a chiral synthon combined with a chiral auxiliary [(R)- or (S)-1

Synthesis of nonracemic hydroxyglutamic acids

• Dorota G. Piotrowska,
• Iwona E. Głowacka,
• Andrzej E. Wróblewski and
• Liwia Lubowiecka

Beilstein J. Org. Chem. 2019, 15, 236–255, doi:10.3762/bjoc.15.22

• -derived precursors When Garner’s aldehyde (R)-5 prepared from D-serine was subjected to ZnCl2-catalyzed cyclocondensation with Danishefsky's diene a (>9:1) mixture of diastereoisomeric pyranones 6 was formed with the threo isomer 6a prevailing. Oxidative removal of two carbon atoms was followed by formate

• ) NaIO4, RuO2, H2O; c) NaOH, H2O then HCl, H2O; d) CH2N2, ether; e) Me3SiNEt2; f) MeOH, PTSA; g) KMnO4, NaOH, H2O; h) HCl, H2O. Synthesis of (2S,3R)-2 and (2S,3S)-2 from (R)-Garner’s aldehyde. Reagents and conditions: a) H2C=CHCH2MgCl, ZnCl2, THF; b) BnBr, NaH, THF; c) 4-methylmorpholine N-oxide, OsO4

The use of 4,4,4-trifluorothreonine to stabilize extended peptide structures and mimic β-strands

• Yaochun Xu,
• Isabelle Correia,
• Tap Ha-Duong,
• Nadjib Kihal,
• Jean-Louis Soulier,
• Julia Kaffy,
• Benoît Crousse,
• Olivier Lequin and
• Sandrine Ongeri

Beilstein J. Org. Chem. 2017, 13, 2842–2853, doi:10.3762/bjoc.13.276

• -catalyzed selective hydrogenation, and oxidation. Zeng et al. described the synthesis of the enantiomer (2R,3S)-Boc-CF3-Thr(Bzl) in four steps from the (S)-Garner’s aldehyde [17][18]. The enantiomer (2S,3R)-Boc-CF3-Thr(Bzl) was not described by Zeng et al. However, we decided to follow this more

• straightforward methodology and we have adapted Zeng’s synthesis starting from the (R)-Garner’s aldehyde. (2S,3R)-Boc-CF3-Thr(Bzl) was obtained with satisfactory yields (Scheme 1). In this synthetic pathway, the key intermediate 6 was obtained, as a mixture of two diastereoisomers (9:1, evaluated by 19F NMR) via

• a nucleophilic trifluoromethylation reaction of Ruppert’s reagent on the (R)-Garner’s aldehyde 5 in THF and in the presence of a catalytic amount of TBAF. Benzylation of the alcohol of 6 was then performed to obtain the desired intermediate as two diastereoisomers 7a and 7b that were easily

Solution-phase automated synthesis of an α-amino aldehyde as a versatile intermediate

• Hisashi Masui,
• Sae Yosugi,
• Shinichiro Fuse and
• Takashi Takahashi

Beilstein J. Org. Chem. 2017, 13, 106–110, doi:10.3762/bjoc.13.13

• -8503, Japan 10.3762/bjoc.13.13 Abstract A solution-phase automated synthesis of the versatile synthetic intermediate, Garner’s aldehyde, was demonstrated. tert-Butoxycarbonyl (Boc) protection, acetal formation, and reduction of the ester to the corresponding aldehyde were performed utilizing our

• originally developed automated synthesizer, ChemKonzert. The developed procedure was also useful for the synthesis of Garner’s aldehyde analogues possessing fluorenylmethyloxycarbonyl (Fmoc) or benzyloxycarbonyl (Cbz) protection. Keywords: acetal formation; amino acid; automated synthesis; Garner’s aldehyde

• developed solution-phase automated synthesizer, ChemKonzert [9]. Protected α-amino aldehydes are versatile intermediates for the synthesis of vicinal amino alcohols and important building blocks for various bioactive natural products [10][11][12]. In particular, Garner’s aldehyde (4a) is very useful as a

Enduracididine, a rare amino acid component of peptide antibiotics: Natural products and synthesis

• Darcy J. Atkinson,
• Briar J. Naysmith,
• Daniel P. Furkert and
• Margaret A. Brimble

Beilstein J. Org. Chem. 2016, 12, 2325–2342, doi:10.3762/bjoc.12.226

• al.: In 2010, Nieuwenhze and Oliver reported a synthesis of protected β-hydroxyenduracididines 40 and 41 making use of intermediate nosylamine 42 (Scheme 6) [57]. The synthesis of 42 began with alkene 43, available from (S)-Garner’s aldehyde. Cleavage of the protecting group allowed installation of

• to orthogonally protected amino acids 46 and 47 (Scheme 7) [58]. Installation of the C-2 stereocentre again began with Garner’s aldehyde 48 and Wittig olefination, followed by Sharpless dihydroxylation to stereoselectively afford diol 49 [59][60]. The C-2 epimer was accessed via Still–Gennari

Synthesis of the C8’-epimeric thymine pyranosyl amino acid core of amipurimycin

• Pramod R. Markad,
• Navanath Kumbhar and
• Dilip D. Dhavale

Beilstein J. Org. Chem. 2016, 12, 1765–1771, doi:10.3762/bjoc.12.165

• , Garner and co-workers have exploited a cycloaddition pathway between a poly-oxygenated diene and Garner’s aldehyde for constructing the carbohydrate core of amipurimycin [9]. Recently, Datta and co-workers reported the first synthesis of a fully-functionalized thymine analogue of amipurimycin, utilizing

One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters

• Gastón Silveira-Dorta,
• Sergio J. Álvarez-Méndez,
• Víctor S. Martín and
• José M. Padrón

Beilstein J. Org. Chem. 2016, 12, 957–962, doi:10.3762/bjoc.12.94

• and threonine, additional O-protection and O-deprotection steps are required (Figure 1). Thus, Garner’s aldehyde [12][13] or N- and O-protected amino ester derivatives have been required [14]. All those methodologies involve long reaction sequences, including protection–deprotection and/or oxidation

Amino acid motifs in natural products: synthesis of O-acylated derivatives of (2S,3S)-3-hydroxyleucine

• Oliver Ries,
• Martin Büschleb,
• Markus Granitzka,
• Dietmar Stalke and
• Christian Ducho

Beilstein J. Org. Chem. 2014, 10, 1135–1142, doi:10.3762/bjoc.10.113

• acyclic D-serinal derivatives for the addition of nucleophiles to amino acid-derived aldehydes [33][34]. However, Zhu and co-workers have pointed out that Garner’s aldehyde surprisingly furnishes the syn diastereomer as the major product from its reaction with isopropyl magnesium chloride [32], thus

A unified approach to the important protein kinase inhibitor balanol and a proposed analogue

• Tapan Saha,
• Ratnava Maitra and
• Shital K. Chattopadhyay

Beilstein J. Org. Chem. 2013, 9, 2910–2915, doi:10.3762/bjoc.9.327

• developed using an efficient fragment coupling protocol which proceeded in good overall yield. Keywords: azepane; balanol; Garner’s aldehyde; PKC inhibitor; ring-closing metathesis; Introduction Protein kinase C (PKC) is a family of phospholipid-dependent kinases that phosphorylate serine and threonine

• preliminary report [62]. Thus, reductive amination of Garner’s aldehyde 17 (Scheme 2) with allylamine produced amine 18 which was N-protected with CbzCl to obtain 19 in an overall yield of 89% over three steps. The oxazolidine ring in compound 19 was then cleaved under acidic conditions and the resulting

Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products

• Mikko Passiniemi and
• Ari M.P. Koskinen

Beilstein J. Org. Chem. 2013, 9, 2641–2659, doi:10.3762/bjoc.9.300

• Mikko Passiniemi Ari M.P. Koskinen Aalto-University, School of Chemical Technology, Department of Chemistry P.O. Box 16100 (Kemistintie 1), FI-00076 Aalto, Finland 10.3762/bjoc.9.300 Abstract Since its introduction to the synthetic community in 1984, Garner’s aldehyde has gained substantial

• deleterious epimerization of the existing stereocenter in Garner’s aldehyde. Keywords: asymmetric synthesis; Garner’s aldehyde; natural product synthesis; L-serine; Introduction “The universe is a dissymmetrical whole. I am inclined to think that life, as manifested to us, must be a function of the

• for the introduction of chirality to substrates. This review presents a general overview of the synthesis and use of Garner’s aldehyde in natural product synthesis. Particular attention will be paid on the preservation of chiral information in the addition reaction of nucleophiles to the aldehyde

Gold-catalyzed oxycyclization of allenic carbamates: expeditious synthesis of 1,3-oxazin-2-ones

• Benito Alcaide,
• Pedro Almendros,
• M. Teresa Quirós and
• Israel Fernández

Beilstein J. Org. Chem. 2013, 9, 818–826, doi:10.3762/bjoc.9.93

• , alkynylcarbamates 1a–g were prepared through reductive amination of the appropriate aldehyde with propargylamine, followed by Boc2O treatment of the corresponding N-substituted prop-2-yn-1-amine. Alkynylcarbamate 1h was prepared from Garner’s aldehyde following a literature report [56][57]. Alkynylcarbamate 1i was

A new approach toward the total synthesis of (+)-batzellaside B

• Jolanta Wierzejska,
• Shin-ichi Motogoe,
• Yuto Makino,
• Tetsuya Sengoku,
• Masaki Takahashi and
• Hidemi Yoda

Beilstein J. Org. Chem. 2012, 8, 1831–1838, doi:10.3762/bjoc.8.210

• corresponding alcohol, which was then subjected to reaction with 2,2-dimethoxypropane (2,2-DMP) in the presence of BF3·Et2O [24] to produce N,O-acetonide 10 in 93% yield over two steps. For the preparation of the E-isomer of α,β-unsaturated ester 11, Wittig–Horner reaction employing Garner’s aldehyde has been

Metathesis access to monocyclic iminocyclitol-based therapeutic agents

• Ileana Dragutan,
• Valerian Dragutan,
• Carmen Mitan,
• Hermanus C.M. Vosloo,
• Lionel Delaude and
• Albert Demonceau

Beilstein J. Org. Chem. 2011, 7, 699–716, doi:10.3762/bjoc.7.81

• . The 3-epi-fagomine (126) could also be obtained from the RCM product 125 (by conventional dihydroxylation/deprotection; 10 steps from Garner’s aldehyde 69). Adenophorine (α-1-deoxy-1-C-methylhomonojirimycin) is a further important iminocyclitol in whose synthesis RCM proved helpful. (+)-Adenophorine

• position of hydroxy substituents is critical for selectivity. In the seminal work by Lebreton and coworkers [73], the first asymmetric total synthesis of (+)-adenophorine was achieved in 14 steps (3.5% overall yield, Scheme 23), starting from the Garner’s aldehyde 69. RCM is essential for construction of