76023-93-3

Upstream product

• 130322-93-9 (5S)-5-hydroxymethyl-2-methylene-5-tetradecanolide 
• 212072-60-1 (4S)-4-(3-ethoxycarbonylbutyl)-2,2-dimethyl-4-nonyl-1,3-dioxolane 
• 105122-27-8 methyl (2RS)-2-methyl-4-<(4R)-4-nonyl-2-phenyl-1,3-dioxolan-4-yl>butanolate 
• 75989-78-5 (5S)-5-tert-butyldimethylsilyloxymethyl-5-tetradecanolide 
• 74-88-4 methyl iodide 
• 487001-49-0 (5S)-2-methyl-5-hydroxymethyltetradec-2-en-5-olide 
• 371231-70-8 (S)-6-Benzyloxymethyl-3-methyl-6-nonyl-tetrahydro-pyran-2-one 
• 202269-17-8 4-Methyl-1-nonyl-6,8-dioxabicyclo[3.2.1]octane 
• 202269-11-2 ((S)-6-Methoxy-5-methyl-2-nonyl-tetrahydro-pyran-2-yl)-methanol 
• 202269-15-6 Acetic acid (S)-5-methyl-2-nonyl-6-oxo-tetrahydro-pyran-2-ylmethyl ester 
• 71582-84-8 (S)-5-Hydroxy-5-hydroxymethyl-2-methyl-tetradecanoic acid 

Downstream Products

• 71582-80-4 (-)-malyngolide 

Relevant academic research and scientific papers

Asymmetric synthesis of quaternary centers. Total synthesis of (-)-malyngolide.

[structure] The deracemization of 3-nonyl-3,4-epoxybut-1-ene with Pd(0) in the presence of chiral ligands using p-methoxybenzyl alcohol as a nucleophile proceeds regio- and enantioselectively to form the monoprotected vinylglycidol in 99% ee. This chiral building block was converted in seven steps to (-)-malyngolide, an antibiotic showing significant activity against Mycobacterium smegmatis and Streptococcus pyogenes. An interesting aspect involves controlling the diastereoselectivity of protonation of an enolate via a distal hydroxyl group.

D- and L-erythrose as sources of chiral quaternary carbon centers. Total synthesis of (-)-malyngolide and (+)-tanikolide

A highly efficient and versatile approach was applied for the total synthesis of the marine natural products (-)-malyngolide and (+)-tanikolide from isopropylidene L- and D-erythrose, using a common strategy.

Enantioselective total synthesis of δ-lactonic marine natural products, (+)-tanikolide and (-)-malyngolide, via RCM reaction

Enantioselective total synthesis of δ-lactonic marine natural products, (+)-tanikolide and (-)-malyngolide isolated from Lyngbya majuscula, was achieved by using the Sharpless asymmetric epoxidation and a ring-closing metathesis, as key reactions.

Efficient 1,8- and 1,9-asymmetric inductions in the Grignard reaction of δ- and ε-keto esters of 1,1′-binaphthalen-2-ols with an oligoether tether as the 2′-substituent: Application to the synthesis of (-)-malyngolide

Efficient 1,8- and 1,9-asymmetric inductions in the Grignard reaction of podand-type δ- (3,4) and ε-keto esters (5,6) are achieved in the presence of MgBr2·OEt2 with up to 97 and 82% optical yields, respectively, by using 2′-[3-(2-methoxyethoxy)propoxy]-1,1′-binaphthalen-2-ol as the chiral auxiliary. The 1,8-asymmetric inductive Grignard reaction has been advantageously utilized in the key step of a synthesis of (-)-malyngolide.

Asymmetric hetero Diels-Alder route to quaternary carbon centers: Synthesis of (-)-malyngolide

Conformationally constrained chiral bis(oxazoline)-metal complex catalyzed asymmetric hetero Diels-Alder reactions of Danishefsky's diene and a variety of α-keto esters constructed quaternary carbon centers enantioselectively. The reaction was utilized in

Alternative synthesis of (-)-malyngolide utilizing (-)-quinic acid

(-)-Malyngolide, an antibiotic isolated from a blue-green algae, was synthesized starting from (-)-quinic acid.

Synthesis of (-)-malyngolide using reactions of alkylidenecarbenes

An alkylidenecarbene has been generated by the reaction of dimethyl (diazomethyl)phosphonate (DAMP), Bu'OK and methyl ketone 6, which itself has been derived from D-mannitol in high yield. The carbene undergoes an intramolecular 1,5 C-H insertion reaction to give the chiral cyclopentane derivative 3 in good yield. It has been found that the same conversion can be conveniently carried out on a large scale with lithiotrimethylsilyldiazomethane. The double bond of 3 has been cleaved to give the keto aldehyde 2, which has been subjected to a double C1 elongation reaction via alkylidenecarbenes using DAMP and K2CO3. The resulting alkyne has been alkylated to give an intermediate 11 which has the carbon skeleton of malyngolide. Deprotection of 11, followed by elaboration of the functional groups completes the chiral synthesis of (-)-malyngolide 1.

Novel Synthesis of (-)-Malyngolide using Reactions of Alkylidene Carbenes

(-)-Malyngolide has been synthesized using three different reactions of alkylidene carbenes, generated by alkenation of carbonyl compounds with dimethyl diazomethylphosphonate.

Stereoselective synthesis of marine antibiotic (-)-malyngolide and its stereoisomers.

A convenient synthetic method for the marine antibiotic (-)-malyngolide and its stereoisomers was accomplished from a chiral alpha-alkoxyketone (4), which was readily available as a chiron. Chiral quaternary carbon synthons (5a) and (5b) as the key intermediates were constructed by the chelation controlled addition of Grignard reagent to 4. The diastereomeric mixture of 5a and 5b was readily transformed into a separable mixture of lactones (7a) and (7b), each of which could be easily separated by silica-gel column chromatography. (-)-Malyngolide and its three stereoisomers were obtained in optically pure form without the need for optical resolution.