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Keywords:

  • alkylation;
  • carbocations;
  • Macmillan catalysts;
  • Mayr’s scale;
  • organocatalysis

Abstract

The organocatalytic stereoselective alkylation of aldehydes is carried out with the four stable carbocations 1, 2, 3, 4 in the presence of a catalytic amount (20 mol%) of MacMillan imidazolidinones 5, 6. In all reactions, lutidine was used as a base. The alkylation reactions are investigated at different temperatures with linear and branched aldehydes. In the case of carbocation tropylium fluoroborate, an interesting reversal of alkylation product configuration was observed, which is driven by entropic effects in the reaction. The absolute configuration of the products obtained is determined by chemical correlation and found to be in general agreement with the model proposed by MacMillan to justify the stereoselectivity obtained in the reactions promoted by catalysts of type 5, 6.

La reazione organocatalitica di alchilazione stereoselettiva di aldeidi è stata condotta con i quattro carbocationi stabili 1, 2, 3, 4 in presenza di quantità catalitiche (20 mol %) degli imidazolidinoni di MacMillan 5, 6. In tutte le reazioni un equivalente di lutidina è stato usato come base. Le reazioni di alchilazione sono state investigate a diverse temperature con aldeidi lineari e ramificate. Nel caso del carbocatione 1 (tropilio tetrafluoroborato) si è osservato un interessante inversione di configurazione del prodotto di alchilazione, determinato da effetti entropici della reazione. La configurazione assoluta dei prodotti ottenuti è stata determinata attraverso una correlazione chimica ed è risultata essere in accordo al modello generale proposto da MacMillan per giustificare la stereoselezione ottenuta nelle reazioni organocatalitiche promosse dai catalizzatori del tipo 5, 6.

Featured Compounds

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  1. 1 - 33
Compound 1
Molecular Weight:177.935
Molecular Formula:C7H7BF4
InChIKey:SQVQHTIKOZVGLR-UHFFFAOYSA-N
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Compound 2
Molecular Weight:340.167
Molecular Formula:C17H21BF4N2
InChIKey:XRCLJMFDDFUJQK-UHFFFAOYSA-N
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Compound 3
Molecular Weight:321.1563
Molecular Formula:C14H12IN
InChIKey:BJHOZJGCQBGXHT-UHFFFAOYSA-M
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Compound 4
Molecular Weight:356.316
Molecular Formula:C16H12F3O4S
InChIKey:SSCJSGXJQUUKNZ-UHFFFAOYSA-M
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Compound 5
Molecular Weight:360.3713
Molecular Formula:C17H23F3N2O3
InChIKey:PSURRFOPVPJWSP-QMDUSEKHSA-N
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Compound 6
Molecular Weight:413.4669
Molecular Formula:C22H27N3O5
InChIKey:VWYSBJYQLCXRGE-QMDUSEKHSA-N
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Compound 7
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 9
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 8a
Molecular Weight:218.3346
Molecular Formula:C15H22O
InChIKey:FOXGQCVRWLQLKS-OAHLLOKOSA-N
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Compound 8b
Molecular Weight:176.2548
Molecular Formula:C12H16O
InChIKey:ZMOZOOSQTYTQBJ-LBPRGKRZSA-N
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Compound 8c
Molecular Weight:224.2976
Molecular Formula:C16H16O
InChIKey:FNJKTFIKBDDZML-MRXNPFEDSA-N
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Compound 8d
Molecular Weight:162.2283
Molecular Formula:C11H14O
InChIKey:QSTZPHQCHBJKGU-SNVBAGLBSA-N
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Compound 7a
Molecular Weight:128.212
Molecular Formula:C8H16O
InChIKey:NUJGJRNETVAIRJ-UHFFFAOYSA-N
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Compound 7b
Molecular Weight:86.1323
Molecular Formula:C5H10O
InChIKey:YGHRJJRRZDOVPD-UHFFFAOYSA-N
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Compound 7c
Molecular Weight:134.1751
Molecular Formula:C9H10O
InChIKey:YGCZTXZTJXYWCO-UHFFFAOYSA-N
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Compound 7d
Molecular Weight:72.1057
Molecular Formula:C4H8O
InChIKey:ZTQSAGDEMFDKMZ-UHFFFAOYSA-N
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Compound 8
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 7e
Molecular Weight:58.0791
Molecular Formula:C3H6O
InChIKey:NBBJYMSMWIIQGU-UHFFFAOYSA-N
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Compound 9a
Molecular Weight:380.5661
Molecular Formula:C25H36N2O
InChIKey:NPKZFLBLVZYERI-JOCHJYFZSA-N
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Compound 9b
Molecular Weight:338.4864
Molecular Formula:C22H30N2O
InChIKey:KPPSJNACDSCNNE-NRFANRHFSA-N
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Compound 9d
Molecular Weight:324.4598
Molecular Formula:C21H28N2O
InChIKey:LKAOSTZWHGXFFR-MRXNPFEDSA-N
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Compound 9e
Molecular Weight:310.4332
Molecular Formula:C20H26N2O
InChIKey:OJOXIZQMRIYCGQ-OAHLLOKOSA-N
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Compound 10
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 10a
Molecular Weight:321.4559
Molecular Formula:C22H27NO
InChIKey:FMZPLIRYSUVPFX-QGZVFWFLSA-N
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Compound 10b
Molecular Weight:279.3761
Molecular Formula:C19H21NO
InChIKey:MCTZRJILKUCPNO-INIZCTEOSA-N
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Compound 10c
Molecular Weight:327.4189
Molecular Formula:C23H21NO
InChIKey:WNFIZBQGJWXZLI-GOSISDBHSA-N
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Compound 10d
Molecular Weight:265.3496
Molecular Formula:C18H19NO
InChIKey:DUUBLEOIVLMBRF-CYBMUJFWSA-N
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Compound 11
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 11a
Molecular Weight:334.4513
Molecular Formula:C23H26O2
InChIKey:SOYIWBJJFSOBNO-UHFFFAOYSA-N
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Compound 11b
Molecular Weight:292.3716
Molecular Formula:C20H20O2
InChIKey:NJNSTBXUOOVMFG-UHFFFAOYSA-N
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Compound 12
Molecular Weight:309.3591
Molecular Formula:C19H19NO3
InChIKey:GFQBCYYAHUQREW-KRWDZBQOSA-N
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Compound I
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 13
Molecular Weight:164.2441
Molecular Formula:C11H16O
InChIKey:ZUFITODNPVLKEA-SNVBAGLBSA-N
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  1. 1 - 33