Phytochemistry Reviews

, Volume 12, Issue 4, pp 603–651

Synthetic approaches to polycyclic semiochemicals and their derivatives: combinatorial methods towards phytochemicals

Authors

  • Nicole Jung
    • Institute of Organic ChemistryKarlsruhe Institute of Technology (KIT)
    • Institute of Toxicology and GeneticsKarlsruhe Institute of Technology (KIT)
  • Franziska Gläser
    • Institute of Organic ChemistryKarlsruhe Institute of Technology (KIT)
    • Institute of Organic ChemistryKarlsruhe Institute of Technology (KIT)
    • Institute of Toxicology and GeneticsKarlsruhe Institute of Technology (KIT)
Article

DOI: 10.1007/s11101-013-9298-0

Cite this article as:
Jung, N., Gläser, F. & Bräse, S. Phytochem Rev (2013) 12: 603. doi:10.1007/s11101-013-9298-0
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Abstract

Semiochemicals are natural products occurring in plants, bacteria or animals which function as carriers of a special message. Depending on the mode of function of the semiochemicals, they are divided into pheromones that trigger a response in members of the same species and allelochemicals (kairomones, allomones) that act between individuals of different species. Semiochemicals are very important compounds that influence the behavior of plants and animals and their adaption to a changing environment. As their importance for plants, animals and the ecological system itself is huge, the synthetic access to these chemicals, their precursors and derivatives is of high interest. Beyond novel strategies for the construction of semiochemical skeletons, combinatorial methods have been implemented to synthesize medium-sized and large-sized libraries that enable diverse modifications of the active compounds. These combinatorial approaches allow the screening for more active compounds and they elucidate the mode of action of the semiochemical or of the biological target. This review summarizes the state of the art procedures for the synthesis of important skeletons appearing in semiochemicals and gives special synthetic procedures for selected examples if the procedure is suitable for a general transfer to the synthesis of derivatives. The synthetic examples are given in the context of known active phytochemicals and their function that allows an evaluation of the given procedures with respect to the fulfillment of the common structural requirements (the structural diversity and flexibility) and the importance for the regulation of biological systems. Parts of this review were given in a lecture at the BioCom 12 in Cadiz, 2012.

Keywords

Combinatorial synthesisIndole alkaloidsNatural productsOxygen heterocyclesSolid-phase synthesis

Abbreviations

DMF

Dimethylformamide

n-BuLi

n-Butyl lithium

TMEDA

Tetramethylethylenediamine

CB1

Cannabinoid receptor 1

CB2

Cannabinoid receptor 2

cAMP

Cyclic adenosine monophosphate

THC

9–Tetrahydrocannabinol

4-HSA

4-Hydroxysalicylaldehyde

HAL

Hypersensitive acid-labile

BAP

6-Benzyl aminopurine

Boc

Di-tert-butyl dicarbonate

BOA

2-Benzoxazolinone

BOMBA

4-Benzyloxy-2-methoxybenzylamine

BINAP

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl

COD

Cyclooctadiene

DMAD

Dimethyl acetylenedicarboxylate

DDQ

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

DBU

1,8-Diazabicyclo[5.4.0]undec-7-ene

DHP

3,4-Dihydro-2H-pyran

DIBOA

2,4-Dihydroxy-1,4-benzoxa-zin-3-one

DIMBOA

2,4-Dihydroxy-7-methoxy-1,4-benzoxazin-3-one

DIPEA

N,N-diisopropylethylamine

DNA

Desoxyribonucleic acid

DOMA

Domino oxa-Michael-aldol

dppp

1,3-Bis(diphenylphosphino)propane

eq./equiv.

Equivalents

Fmoc

Fluorenylmethyloxycarbonyl

GA

Gibberellin

Glc

Glucose

LDA

Lithium diisopropylamide

LiHMDS

Lithium bis(trimethylsilyl)amide

mCPBA

Meta-chloroperoxybenzoic acid

Mes

Mesityl

MW

Microwave irradiation

NMO

N-methylmorpholine-N-oxide

Ph

Phenyl

PG

Protecting group

PPTS

p-Toluenesulfonate

SNAr

Nucleophilic aromatic substitution

TBDAS

Tert-butyldiarylsilyl

TBDMS

Tert-butyldimethylsilyl

TFA

Trifluoroacetic acid

THF

Tetrahydrofuran

TPAP

Tetrapropylammonium perruthenate

TRIAL

Tumor necrosis factor (TNF)-related apoptosis-inducing ligand

tRNA

Transfer ribonucleic acid

rt

Room temperature

Copyright information

© Springer Science+Business Media Dordrecht 2013