Linked Life Data

20429523

Source:http://linkedlifedata.com/resource/pubmed/id/20429523

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
11
pubmed:dateCreated
2010-5-28
pubmed:abstractText
Irradiation of a tryptamine linked through its side-chain nitrogen to an alkylidene malonate residue results in an intramolecular [2 + 2] cycloaddition to the indole 2,3-double bond. The resultant cyclobutane undergoes spontaneous retro-Mannich fission to produce a spiro[indoline-3,3'-pyrrolenine] with relative configuration defined by the orientation of substituents in the transient cyclobutane. The tandem intramolecular photocycloaddition-retro-Mannich process, abbreviated as TIPCARM, leads to a spiropyrrolidine which is poised to undergo a second retro-Mannich fragmentation that expels the malonate unit and generates transiently an indolenine. The latter undergoes rearrangement to a beta-carboline, which upon brominative oxidation undergoes further rearrangement to an oxindole. With tryptamine as starting material, the entire sequence leads to the alkaloid (+/-)-coerulescine. Starting from 5-methoxytryptamine, a parallel series affords (+/-)-horsfiline. Modification of the malonylidene unit to include an isobutyl substituent at C3 affords a photosubstrate which also undergoes the TIPCARM process. In this case, a 2'-isobutyl-substituted spiro[indoline-3,3'-pyrrolenine] results. This undergoes stereoselective hydride reduction to give a product with relative orientation at the spiro carbon and the new stereocenter bearing the isobutyl appendage corresponding to that of the alkaloid elacomine. From tryptamine, the sequence paralleling that leading to coerulescine and horsfiline terminates at 6-deoxyelacomine, whereas 6-methoxytryptamine as starting material affords (+/-)-elacomine itself.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jun
pubmed:issn
1520-6904
pubmed:author
pubmed:issnType
Electronic
pubmed:day
4
pubmed:volume
75
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3569-77
pubmed:meshHeading
pubmed:year
2010
pubmed:articleTitle
Tandem intramolecular photocycloaddition-retro-Mannich fragmentation as a route to spiro[pyrrolidine-3,3'-oxindoles]. Total synthesis of (+/-)-coerulescine, (+/-)-horsfiline, (+/-)-elacomine, and (+/-)-6-deoxyelacomine.
pubmed:affiliation
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331-4003, USA. james.white@oregonstate.edu
pubmed:publicationType
Journal Article, Research Support, N.I.H., Extramural