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Review
. 2007 Dec 3;2(12):1476-91.
doi: 10.1002/asia.200700183.

Enantioselective Tsuji allylations

Justin T Mohr  1 , Brian M Stoltz
Affiliations
Review

Enantioselective Tsuji allylations

Justin T Mohr et al. Chem Asian J. .

Abstract

The family of allylation reactions developed by Tsuji in the 1980s are capable of generating tertiary and quaternary carbon stereocenters from several synthetic precursors. Despite the utility of these transformations, they have seen little use in the synthesis of natural products. Recently, the power of these reactions was significantly enhanced by the development of enantioselective versions of these transformations. Applications of these methods to the enantioselective syntheses of natural products and pharmaceutical compounds highlight the importance of these developments.

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Figures

Scheme 1
Scheme 1
a) Enantioselective allylic alkylation with stabilized enolates. b) Enantioselective allylic alkylation with unstabilized enolates.
Scheme 2
Scheme 2
Tsuji allylation reactions. (dba = dibenzylideneacetone; TMS = trimethylsilyl; DPPE = bis(diphenylphosphino)ethane)
Scheme 3
Scheme 3
Regiochemical fidelity in the Tsuji allylation.
Scheme 4
Scheme 4
Enantioenriched cycloalkanones produced from allyl enol carbonates.
Scheme 5
Scheme 5
Enantioenrichment of ketone (–)-1 via the semicarbazone derivative.
Scheme 6
Scheme 6
Enantioenriched cycloalkanones produced from allyl enol carbonates.
Scheme 7
Scheme 7
Enantioenriched ketones produced from (Z)-enol carbonates.
Scheme 8
Scheme 8
Reactivity differences for (E)- and (Z)-enol carbonates. (N.D. = not determined)
Scheme 9
Scheme 9
Allylic alkylation from isomeric silyloxy substituted allyl enol carbonates. (TBS = tert-butyldimethylsilyl)
Scheme 10
Scheme 10
Allylic alkylation to form α-silyloxy aldehydes and ketones.
Scheme 11
Scheme 11
Enantioenriched cycloalkanones produced from silyl enol ethers.
Scheme 12
Scheme 12
Non-selective enolization leads to mixtures of allylated products.
Scheme 13
Scheme 13
Enantioselective decarboxylative allylation with an allyl β-ketoester.
Scheme 14
Scheme 14
Enantioenriched cycloalkanones prepared from allyl β-ketoesters. (TBDPS = tert-butyldiphenylsilyl)
Scheme 15
Scheme 15
Enantioselective cascade allylation generating two quaternary stereocenters.
Scheme 16
Scheme 16
Vinylogous thioesters prepared from allyl β-ketoesters.
Scheme 17
Scheme 17
Allylation in the presence of a pendent 1,3-diester.
Scheme 18
Scheme 18
Enantioselective Tsuji allylation in the total synthesis of (+)-dichroanone. (DMA = N,N-dimethylacetamide)
Scheme 19
Scheme 19
Enantioselective formal synthesis of (S)-oxybutynin. (HMDS = hexamethyldisilazane)
Scheme 20
Scheme 20
Progress toward the total synthesis of zoanthenol. (Boc = tert-butyloxycarbonyl; DMAP = 4-(dimethylamino)pyridine; LDA = lithium diisoproylamide; Tf = trifluoromethanesulfonyl; Cy = cyclohexyl; TBAF = tetrabutylammonium fluoride)
Scheme 21
Scheme 21
Enantioenriched α-fluoroketones derived from allyl β-ketoesters.
Scheme 22
Scheme 22
Enantioenriched α-fluorocycloalkanones prepared from allyl β-ketoesters. (N.D. = not determined)
Scheme 23
Scheme 23
Enantioenriched α-fluorocycloalkanones prepared from silyl enol ethers.
Scheme 24
Scheme 24
Asymmetric ring-expanding allylation.
Scheme 25
Scheme 25
a) Transformations of ketone (–)-1. b) Ring closing metathesis generating a spirocycle.
Scheme 26
Scheme 26
Stork-Danheiser type transformations of vinylogous thioester (R)-51.
Scheme 27
Scheme 27
a) Trost's crossover experiment. b) Stoltz’ crossover experiment.
Scheme 28
Scheme 28
Possible catalytic cycle for decarboxylative allylation.
See this image and copyright information in PMC

References

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