Concise asymmetric synthesis of (-)-sparteine

Chemical Communications

Volumn , Issue 16, 2004, Pages 1830-1831

  Hermet, Jean Paul R ^a   McGrath, Matthew J ^a   O'Brien, Peter ^a   Porter, David W ^a   Gilday, John ^b  

^a UNIVERSITY OF YORK   (United Kingdom)

^b ASTRAZENECA   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALPHA,BETA AMINO ESTER; ESTER DERIVATIVE; ETHYL 7 IODOHEPT 2 ENOATE; SPARTEINE; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC SYNTHESIS; CHIRALITY; DRUG STRUCTURE; DRUG SYNTHESIS; MICHAEL ADDITION;

EID: 4644225378     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b406632d     Document Type: Article

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23. N2 substitution of the iodide precedes the cyclisation and hence, two competing transition states for cyclisation can be constructed: A → 7 and B → 8. In both A and B, the α-methylbenzyl substituent is arranged so that the hydrogen occupies the most sterically hindered "inside" position. The major product 7 arises from transition state A in which the larger phenyl group minimises its steric clash with the axial hydrogen on C*. We briefly investigated the use of other chiral amines but were unable to improve on the 2:1 stereoselectivity.
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30. In a model study, enolate 11 added to ent-10 to give 83% of a ∼ 9:1 diastereomeric mixture of Michael adducts (major assigned as 12 based on the relative stereocontrol in the (-)-sparteine synthesis).