Total synthesis of (±)-α-isosparteine, (±)-β- isosparteine, and (±)-sparteine from a common tetraoxobispidine intermediate

Journal of Organic Chemistry

Volumn 73, Issue 20, 2008, Pages 7939-7951

  Norcross, Neil R ^b   Melbardis, John P ^a   Solera, Margarita Ferris ^b   Sephton, Mark A ^a   Kilner, Colin ^b   Zakharov, Lev N ^a   Astles, Peter C ^c   Warriner, Stuart L ^b   Blakemore, Paul R ^a  

^a OREGON STATE UNIVERSITY   (United States)

^b UNIVERSITY OF LEEDS   (United Kingdom)

^c ELI LILLY AND COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACIDS; CHEMICAL REACTIONS; OLEFINS; SODIUM; SYNTHESIS (CHEMICAL);

ALLYLATION; BIS IMIDE; CHEMICAL EQUATIONS; GLOBAL REDUCTION; KNOEVENAGEL CONDENSATION; MALONATE; REACTION SEQUENCES; RING-CLOSING OLEFIN METATHESIS; SAKURAI; SODIUM BOROHYDRIDE; SYNTHESIS OF; SYNTHETIC SEQUENCES; SYNTHON; TOTAL SYNTHESIS;

CONDENSATION REACTIONS;

1,1,3,3 PROPANETETRACARBOXAMIDE; 3,7 DIALLYL 2,4,6,8 TETRAOXO 3,7 DIAZABICYCLO[3.3.1]NONANE; ALKALOID DERIVATIVE; ALLYLMAGNESIUM BROMIDE; ALPHA ISOSPARTEINE; AMIDE; BETA ISOSPARTEINE; BISHEMIAMINAL; BISIMIDE; BORANE DERIVATIVE; IMIDE; MAGNESIUM DERIVATIVE; MALONIC ACID; NONANE; OXAZABOROLIDINE DERIVATIVE; SPARTEINE; TETRAOXOBISPIDINE; UNCLASSIFIED DRUG; 3,7 DIALLYL 2,4,6,8 TETRAOXO 3,7 DIAZABICYCLO(3.3.1)NONANE; 3,7-DIALLYL-2,4,6,8-TETRAOXO-3,7-DIAZABICYCLO(3.3.1)NONANE; BISPIDINE; FUSED HETEROCYCLIC RINGS;

ALLYLATION; ARTICLE; CHEMICAL REACTION; CYCLIZATION; HYDROGENATION; KNOEVENAGEL CONDENSATION; REACTION ANALYSIS; REDUCTION; RING CLOSING METATHESIS; SYNTHESIS; CHEMICAL STRUCTURE; CHEMISTRY; STEREOISOMERISM;

BICYCLO COMPOUNDS, HETEROCYCLIC; MODELS, MOLECULAR; SPARTEINE; STEREOISOMERISM;

EID: 53849129256     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8013512     Document Type: Article

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163. 3SiH). This plan stalled when the requisite silyl ether derivatives could not be generated.
164. 2-symmetric) regioselectivity to this phenomena. For elaboration on the concept as it relates to the regiodivergent conversion of enantiomers within a racemic mixture by a chiral reagent, see: Kagan, H. B. Croat. Chem. Acta 1996, 69, 669-680.
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167. Carboxylic acid anhydrides represent the best studied substrate class, see: Atodiresei, I.; Schiffers, I.; Bolm, C. Chem. Rev. 2007, 107, 5683-5712.
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179. The illustrated enantiomer of 52 is that anticipated on the basis of the standard Corey model (ref 104c) assuming that only exo-face addition of hydride to 25 is possible, and that the N-benzyl moiety is the more sterically demanding group (as advocated by Speckamp and Hiemstra for related bicyclic mono-imides, ref 101b). Almost identical results were obtained with Jones' aminoindanol derived oxazaborolidine (ref 102c) in place of the more common CBS-catalyst 51. In this case, reduction of 25 with the B-methyl oxazaborolidine derived from (1R,2S)-cis-1-amino- 2-indanol gave the opposite enantiomer of 52 to that generated from the (S)-prolinol derived catalyst 51, but also in ca. 70% ee.
180. Stead, D.; O'Brien, P.; Sanderson, A. Org. Lett. 2008, 10, 1409-1412.