Chiral bispidines

Synthesis

Volumn , Issue 18, 2008, Pages 2841-2867

  Breuning, Matthias ^a   Steiner, Melanie ^a  

^a UNIVERSITY OF WÜRZBURG   (Germany)

Author keywords

( ) sparteine; Asymmetric synthesis; Bicyclic compounds; Chiral auxiliaries; Chiral bispidines

Indexed keywords

(-)-SPARTEINE; ASYMMETRIC SYNTHESIS; BICYCLIC COMPOUNDS; CHIRAL AUXILIARIES; CHIRAL BISPIDINES;

KETONES;

BISPIDINE; CHEMICAL COMPOUND; DIETHYLZINC; PIPERIDINE DERIVATIVE; SPARTEINE; UNCLASSIFIED DRUG;

ASYMMETRIC SYNTHESIS; ATOM; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; ENANTIOSELECTIVITY; NOMENCLATURE; REVIEW; STEREOCHEMISTRY;

EID: 53249138235     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1067241     Document Type: Review

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184. (b) Coldham, I.; Dufour, S.; Haxell, T. F. N.; Patel, J. J.; Sanchez-Jimenez, G. J. Am. Chem. Soc. 2006, 128, 10943.
185. The high configurational stability of α-lithio N-Boc- pyrrolidine is also obvious from the following experiment: (S)- tributylstannyl N-Boc-pyrrolidine (96% ee), subjected to a tin-lithium exchange using s-BuLi or s-BuLi-TMEDA, gives, after electrophilic trapping with TMSC1, 12 in 93% ee (15% yield) or 74% ee (36% yield), respectively; see ref. 15.
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190. 48 was performed with 134 leading to 12.
191. Deprotonation of 11 with 1.3 equivalents of 8-s-BuLi and 1.3 equivalents of 5-s-BuLi gave, after trapping with TMSC1, ent-12 in 80% ee, thus indicating that 8 is about ten times more reactive than 5, see ref. 29.
192. It should be noted that diminished enantioselectivities in reactions with low conversions might be a consequence of competing deprotonation processes with low stereocontrol that are mediated by other unknown diamine-RLi adducts, which are not of importance if the 'correct' diamine-RLi adduct possesses a decent reactivity.
193. 64 was performed with 78 leading to ent-12.
194. Breuning, M.; Steiner, M. unpublished results.
195. In should be mentioned that the formation of prelithiation complexes between the ligand 131e, s-BuLi, and other substrates is very probable, since 131e gives acceptable to good yields and enantioselectivities in the deprotonation of the O-alkyl carbamate 179 and the phosphine boranes 17, 181, and 182 (see Section 3.3).
196. + complexes of the following diamines have been used: 5, ent-8, 78, ent-134, 148 (see Figure 3), ent-36, ent-53, ent-64 (see Figure 5), 166, 175, 176a, 176c, and ent-176b (see Figure 7).
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