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Volumn 17, Issue 16, 2011, Pages 4480-4495

Synthesis of 1,2-amino alcohols by sigmatropic rearrangements of 3-(N-Tosylamino)allylic alcohol derivatives

Author keywords

amino alcohols; diastereoselectivity; enamides; sigmatropic rearrangements; Wittig rearrangement

Indexed keywords

AMINO ALCOHOLS; DIASTEREOSELECTIVITY; ENAMIDES; SIGMATROPIC REARRANGEMENTS; WITTIG REARRANGEMENT;

EID: 79953710543     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201003265     Document Type: Article
Times cited : (27)

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    • The stereochemical outcome of the [2,3]-Wittig rearrangement of amides 27b-e was assumed to be similar to 27a. The syn relative orientation of the hydroxyl and amino groups in 28f was ascertained by a chemical correlation as described for 28a.
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    • However, the organocatalyzed [2,3]-Wittig rearrangement of the α-allyloxy methyl ketone 93 derived from alcohol 3a did not proceed at RT. The rearrangement occurred slowly in refluxing methanol to deliver the rearranged product 94 in very low yield (20%) and as a 80:20 mixture of diastereomers. The presence of the bulky N-benzyl-N-tosylamino at C3 seems to significantly reduce the rate of the organocatalyzed Wittig rearrangement
    • Angew. Chem. Int. Ed. 2006, 45, 2116-2119. However, the organocatalyzed [2,3]-Wittig rearrangement of the α-allyloxy methyl ketone 93 derived from alcohol 3a did not proceed at RT. The rearrangement occurred slowly in refluxing methanol to deliver the rearranged product 94 in very low yield (20%) and as a 80:20 mixture of diastereomers. The presence of the bulky N-benzyl-N-tosylamino at C3 seems to significantly reduce the rate of the organocatalyzed Wittig rearrangement.
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    • note
    • Although the configuration of the minor diastereomer 47a was not unambiguously ascertained, fractions containing a mixture of 45a and 47a were apparently converted to same methyl ester by acidic methanolysis. This result seems to confirm that the relationship between the amino and hydroxyl groups in 47a is syn.
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    • note
    • Amide ent- 45a (the enantiomer of 45a prepared by [2,3]-Wittig rearrangement of ent- 44a derived from (1R,2S)-1-aminoindan-2-ol) was transformed to the 2-amino-1,3-diol ent- 95 by ozonolysis of the alkene and subsequent reduction. Acidic methanolysis of ent- 95 occurred with concomittant lactonization to provide the α-hydroxy-β-(N-tosylamino)-γ- lactone 96. On the other hand, when methyl ester 59 was subjected to oxidative cleavage of the alkene followed by reduction, the enantiomer of lactone 96 was obtained. From compound 62, the same 2-amino-1,3-diol ent- 95 was isolated. These experiments enabled the assignment of the absolute configuration of compounds 59 (and 57) and 62.
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    • Alkynes can interfere with dienes RCM
    • Alkynes can interfere with dienes RCM
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    • this problem has occasionally been circumvented by the formation of the alkyne dicobalt hexacarbonyl complex, see
    • C. Bressy, F. Bargiggia, M. Guyonnet, S. Arseniyadis, J. Cossy, Synlett 2009, 565-568; this problem has occasionally been circumvented by the formation of the alkyne dicobalt hexacarbonyl complex, see
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    • note
    • 4, MeOH) gave the anti-2-amino-1,3-diol 80. This compound had also been synthesized from 76a (see Scheme 27).


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