Atroposelective Silylation of 1,1′‐Biaryl‐2,6‐diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution

Zhu, Min; Jiang, Hua-Jie; Sharanov, Illia; Irran, Elisabeth; Oestreich, Martin

doi:10.1002/anie.202304475

Cited by 15 publications

(6 citation statements)

References 39 publications

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“…A catalyst evaluation showed popular IDPi’s to provide insufficient enantioselectivities while our sterically bulky IDPi provided encouraging results (Table entries 1–10). In more detail, catalyst structures 2b , , 2c , 2d , , 2e , 2g , 2h , 2i , 2j have all proved to be valuable in generating a diverse range of chiral compounds with high-levels of stereoselectivity. Ultimately, most of these catalysts has been confirmed to be optimal for at least one reaction type rendering these structures as important benchmarks for evaluating 2a in this reaction.…”

Section: Results and Discussionmentioning

confidence: 99%

A Bulky Imidodiphosphorimidate Brønsted Acid Enables Highly Enantioselective Prins-semipinacol Rearrangements

Lai,

Reid

2024

ACS Catal.

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The development of BINOL-derived Brønsted acid catalysts has been profoundly guided by rational design, with carefully implemented structural changes leading to generations of catalysts with enhanced reaction capabilities. This approach to catalyst optimization has promoted the integration of knowledge gathered in optimizing prior eras of Brønsted acids, and ultimately, the molecular features that have contributed to the success of previous designs are preserved. Of these, the large substituents at the 3 and 3′ positions of the BINOL backbone are the most critical with almost every developed structure possessing this feature. However, imidodiphosphorimidate (IDPi) catalysts are not synthetically well-suited to contain the same sterically bulky groups associated with the high selectivity imparted by previously implemented catalyst structures. Herein, we have leveraged the moderate size of the 9-phenanthryl substituent to synthesize an IDPi with sizable steric demands. The applicability of the catalyst was evaluated in the construction of stereochemically dense spirocycles generated via an asymmetric Prins-semipinacol reaction sequence. Transition state calculations were deployed to interrogate the origins of the high enantioselectivity, and these demonstrate the mechanistic hallmarks of the 9-phenanthryl substituent can be generalized to a genuinely different class of Brønsted acid catalyst. Ultimately, this work provides the basis for the development of general catalyst design principles and the translation of "privileged" substituents across prior eras of Brønsted acid catalysts structures.

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Section: Results and Discussionmentioning

confidence: 99%

A Bulky Imidodiphosphorimidate Brønsted Acid Enables Highly Enantioselective Prins-semipinacol Rearrangements

Lai,

Reid

2024

ACS Catal.

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“…11 12 Thereafter, several groups have reported silylative enantioselective desymmetrization of meso -1,2-diols by using scaffolding catalysts and silyl chlorides, 13 BINOL-based polyether catalyst and hexamethyldisilazane (HDMS), 14 and silylative enantioselective desymmetrization of 1,1′-biaryl-2,6-diols by using Brønsted acid catalyst and HDMS, 15 and Brønsted acid catalyst and allylic silane. 16 17…”

Section: Table 1 Optimization Of the Reaction Condition...mentioning

confidence: 99%

Enantioselective Silylative Desymmetrization of meso-Indane-1,3-diols Catalyzed by Chiral Guanidines

Nakata,

Ui,

Iwakura

et al. 2024

Synlett

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Chiral guanidine-catalyzed desymmetrization of meso-indan-1,3-diols was achieved via enantioselective silylation by using chlorosilanes in good yields with high selectivity. The combination of chlorosilanes and catalysts was determined by the substituents at the C-2 position on the substrate. It was found that the fused phenyl ring on the substrate was essential for achieving high selectivity. The proposed method was found to be applicable to several types of substrates under optimized reaction conditions. Double silylative kinetic resolution with additive Horeau amplification was observed to establish high selectivity.

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“…During our studies, Professor Martin Oestreich kindly shared a manuscript with us describing his independent and advanced investigation of the same transformation. 10 Our own studies on the asymmetric silylation of biaryl diols have since been terminated at the reported stage.…”

Section: Scheme 3 Control Experimentsmentioning

confidence: 99%

Brønsted Acid Catalyzed Asymmetric Silylation of Biaryl Diols

List

Han²,

Zhou

2023

Synlett

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Atroposelective Silylation of 1,1′‐Biaryl‐2,6‐diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution

Cited by 15 publications

References 39 publications

A Bulky Imidodiphosphorimidate Brønsted Acid Enables Highly Enantioselective Prins-semipinacol Rearrangements

A Bulky Imidodiphosphorimidate Brønsted Acid Enables Highly Enantioselective Prins-semipinacol Rearrangements

Enantioselective Silylative Desymmetrization of meso-Indane-1,3-diols Catalyzed by Chiral Guanidines

Brønsted Acid Catalyzed Asymmetric Silylation of Biaryl Diols

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