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Keywords:

  • C[BOND]H activation;
  • density functional calculations;
  • Lewis acids;
  • phosphoric acid;
  • tert-aminocyclization

Abstract

A mechanistic study of the tert-aminocyclization reaction was performed by using DFT calculations and labeling experiments. The results showed that the reaction proceeded through a rate-limiting-, stereospecific-, and suprafacial 1,5-H-transfer pathway, followed by a barrier-less C[BOND]C bond formation. The mode of stereocontrol for facial selection could be ruled out owing to the high activation energy of C[BOND]N bond rotation. The intrinsic feature of this Lewis acid activation was found to be the activation of the LUMO, as well as an intermediate-stabilization effect. The catalytically active species was believed to be a 1:1 complex of phosphoric acid and MgCl2, which was stabilized by a H⋅⋅⋅Cl hydrogen bond. The chiral catalytic complex selectively recognizes and activates one of the two helical conformations of substrate A, required for 1,5-suprafacial H-transfer, which dictates the stereoselectivity of the forming products.

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Featured Compounds

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  1. 1 - 16
Compound 2a
Molecular Weight:572.4424
Molecular Formula:C32H17F4O4P
InChIKey:MYQOFYSGRBDPSP-UHFFFAOYSA-N
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Compound 1
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 3
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 3a
Molecular Weight:351.3957
Molecular Formula:C21H21NO4
InChIKey:YZZYJQGDTVHMGH-SFHVURJKSA-N
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Compound 3b
Molecular Weight:379.4489
Molecular Formula:C23H25NO4
InChIKey:JSPVIBIPAIGUJX-FQEVSTJZSA-N
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Compound 3c
Molecular Weight:345.4327
Molecular Formula:C20H27NO4
InChIKey:AACSJMRTEHCJBL-KRWDZBQOSA-N
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Compound 3d
Molecular Weight:375.5017
Molecular Formula:C22H33NO4
InChIKey:HOLYWUULWVMOFI-IBGZPJMESA-N
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Compound 1a
Molecular Weight:351.3957
Molecular Formula:C21H21NO4
InChIKey:AXOWUWFCPLOEFA-UHFFFAOYSA-N
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Compound MgCl2·1a
Molecular Weight:446.607
Molecular Formula:C21H21Cl2MgNO4
InChIKey:YUALCGUPJOYCCH-UHFFFAOYSA-L
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Compound MgCl2·3a
Molecular Weight:446.607
Molecular Formula:C21H21Cl2MgNO4
InChIKey:MBAURWVVDZFHLA-YTNSDAIYSA-L
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Compound 1e
Molecular Weight:380.4551
Molecular Formula:C23H25NO4
InChIKey:Not Available
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Compound 3e-D
Molecular Weight:380.4551
Molecular Formula:C23H25NO4
InChIKey:Not Available
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Compound 3e-H
Molecular Weight:380.4551
Molecular Formula:C23H25NO4
InChIKey:Not Available
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Compound 1f
Molecular Weight:381.4612
Molecular Formula:C23H25NO4
InChIKey:Not Available
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Compound 1b
Molecular Weight:379.4489
Molecular Formula:C23H25NO4
InChIKey:WYMXDDUDCSULDP-UHFFFAOYSA-N
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Compound 3f
Molecular Weight:381.4612
Molecular Formula:C23H25NO4
InChIKey:Not Available
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