ChemInform Abstract: BIOMIMETIC ENTRY TO ACYCLIC TERPENE SYNTHESIS. A NOVEL REARRANGEMENT OF ALLYL ETHER CATALYZED BY ORGANOALUMINUM REAGENTS

1982 ◽  
Vol 13 (43) ◽  
Author(s):  
Y. YAMAMURA ◽  
K. UMEYAMA ◽  
K. MARUOKA ◽  
H. YAMAMOTO
Keyword(s):  
Allyl Ether ◽  
Terpene Synthesis

Biomimetic entry to acyclic terpene synthesis a novel rearrangement of allyl ether catalyzed by organoaluminium reagents

1982 ◽  
Vol 23 (18) ◽  
pp. 1933-1936 ◽  
Author(s):  
Yoshihiro Yamamura ◽  
Kensuke Umeyama ◽  
Keiji Maruoka ◽  
Hisashi Yamamoto
Keyword(s):  
Allyl Ether ◽  
Terpene Synthesis

scholarly journals Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Guogang Deng ◽  
Shengzu Duan ◽  
Jing Wang ◽  
Zhuo Chen ◽  
Tongqi Liu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Allyl Ether ◽  
Metal Catalyst ◽  
Metal Free ◽  
Allyl Ethers ◽  
Bond Forming ◽  
Allyl Halides ◽  
Synthetic Utility ◽  
Insight Into ◽  
Allyl Esters

AbstractAllylation of nucleophiles with highly reactive electrophiles like allyl halides can be conducted without metal catalysts. Less reactive electrophiles, such as allyl esters and carbonates, usually require a transition metal catalyst to facilitate the allylation. Herein, we report a unique transition-metal-free allylation strategy with allyl ether electrophiles. Reaction of a host of allyl ethers with 2-azaallyl anions delivers valuable homoallylic amine derivatives (up to 92%), which are significant in the pharmaceutical industry. Interestingly, no deprotonative isomerization or cyclization of the products were observed. The potential synthetic utility and ease of operation is demonstrated by a gram scale telescoped preparation of a homoallylic amine. In addition, mechanistic studies provide insight into these C(sp3)–C(sp3) bond-forming reactions.

scholarly journals Enhancing Terpene Yield from Sugars via Novel Routes to 1-Deoxy-d-Xylulose 5-Phosphate

2014 ◽  
Vol 81 (1) ◽  
pp. 130-138 ◽  
Author(s):  
James Kirby ◽  
Minobu Nishimoto ◽  
Ruthie W. N. Chow ◽  
Edward E. K. Baidoo ◽  
George Wang ◽  
...  
Keyword(s):  
Bacterial Species ◽  
Xylose Reductase ◽  
Pentose Phosphate ◽  
Terpene Biosynthesis ◽  
Content Type ◽  
E Coli ◽  
Pathway Expression ◽  
Terpene Synthesis ◽  
Selection For

ABSTRACTTerpene synthesis in the majority of bacterial species, together with plant plastids, takes place via the 1-deoxy-d-xylulose 5-phosphate (DXP) pathway. The first step of this pathway involves the condensation of pyruvate and glyceraldehyde 3-phosphate by DXP synthase (Dxs), with one-sixth of the carbon lost as CO2. A hypothetical novel route from a pentose phosphate to DXP (nDXP) could enable a more direct pathway from C5sugars to terpenes and also circumvent regulatory mechanisms that control Dxs, but there is no enzyme known that can convert a sugar into its 1-deoxy equivalent. Employing a selection for complementation of adxsdeletion inEscherichia coligrown on xylose as the sole carbon source, we uncovered two candidate nDXP genes. Complementation was achieved either via overexpression of the wild-typeE. coliyajOgene, annotated as a putative xylose reductase, or via various mutations in the nativeribBgene.In vitroanalysis performed with purified YajO and mutant RibB proteins revealed that DXP was synthesized in both cases from ribulose 5-phosphate (Ru5P). We demonstrate the utility of these genes for microbial terpene biosynthesis by engineering the DXP pathway inE. colifor production of the sesquiterpene bisabolene, a candidate biodiesel. To further improve flux into the pathway from Ru5P, nDXP enzymes were expressed as fusions to DXP reductase (Dxr), the second enzyme in the DXP pathway. Expression of a Dxr-RibB(G108S) fusion improved bisabolene titers more than 4-fold and alleviated accumulation of intracellular DXP.

Synthesis and thiol-ene photopolymerization of allyl-ether functionalized dendrimers

2007 ◽  
Vol 46 (4) ◽  
pp. 1339-1348 ◽  
Author(s):  
Camilla Nilsson ◽  
Neil Simpson ◽  
Michael Malkoch ◽  
Mats Johansson ◽  
Eva Malmström
Keyword(s):  
Allyl Ether
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