Total synthesis of (±)-terpestacin and (±)-11-epi-terpestacin

Journal of Organic Chemistry

Volumn 72, Issue 17, 2007, Pages 6473-6480

  Berger, Gideon O ^a   Tius, Marcus A ^a,b  

^a UNIVERSITY OF HAWAII   (United States)

^b UNIVERSITY OF HAWAII CANCER CENTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NAZAROV REACTION; STEREOGENIC CARBON ATOMS; TERPESTACIN;

ENANTIOMERS; ETHERS; REACTION KINETICS; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

ORGANIC COMPOUNDS;

11 EPI TERPESTACIN; ALLENE DERIVATIVE; NATURAL PRODUCT; TERPESTACIN; UNCLASSIFIED DRUG; BICYCLO COMPOUND;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; EPIMERIZATION; NAZAROV REACTION; PROTON NUCLEAR MAGNETIC RESONANCE; QUANTUM YIELD; REACTION ANALYSIS; REDUCTION; STEREOCHEMISTRY; SYNTHESIS; CHEMICAL STRUCTURE; CHEMISTRY; ELECTROSPRAY MASS SPECTROMETRY; INFRARED SPECTROPHOTOMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM;

BICYCLO COMPOUNDS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; SPECTROMETRY, MASS, ELECTROSPRAY IONIZATION; SPECTROPHOTOMETRY, INFRARED; STEREOISOMERISM;

EID: 34547957662     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo070923d     Document Type: Article

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39. The chromatographic separation of 27 from 26 is very difficult; therefore, pains must be taken to ensure that the reaction proceeds to completion. The iodomethane was distilled and filtered through basic alumina prior to use. The HMPA must be freshly distilled.
40. 2)
41. The reaction mixture becomes gelatinous so a large stir bar should be used. The reaction has also been performed on a 13 g scale with an overhead stirrer with comparable yields.
42. Diethyl 3-oxo-2-butylphosphonate is the minor impurity but is removed in the final reaction leading to 27.
43. 6 for the product included singlets at 1.70, 1.03, 0.98, 0.20, 0.14, 0.12, 0.10 ppm.
44. 3N scavenged the excess allylic iodide, making the purification easier.
45. Complete stereoselectivity was achieved at Cl, as indicated by the formation of a single diastereomer from the macrocyclization.
46. Iodomethane and HMPA were freshly distilled, and the iodomethane was filtered through basic alumina. The solution was prepared over molecular sieves.
47. 2 approximately every 2.5 min to maintain a temperature of -94°C.