Asymmetric Synthesis of Trisubstituted Vicinal Diols through Copper(I)‐Catalyzed Diastereoselective and Enantioselective Allylation of Ketones with Siloxypropadienes DOI
Nan Jiang,

Pei‐Zhi Liu,

Zhi‐Zhou Pan

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(21)

Опубликована: Фев. 27, 2024

Abstract Chiral trisubstituted vicinal diols are a type of important organic compounds, serving as both common structure units in bioactive natural products and chiral auxiliaries asymmetric synthesis. Herein, by using siloxypropadienes the precursors allyl copper(I) species, copper(I)‐catalyzed diastereoselective enantioselective reductive allylation ketones was achieved, providing syn ‐diols anti good to excellent enantioselectivity. DFT calculations show that cis ‐γ‐siloxy‐allyl copper species generated favorably with either 1‐TBSO‐propadiene or 1‐TIPSO‐propadiene. Moreover, steric difference TBS group TIPS distinguishes face selectivity acetophenone, leading ‐selectivity for Easy transformations were performed, demonstrating synthetic utility present method. one diol prepared above used suitable organocatalyst catalytic self‐coupling aldimines situ B 2 (neo) .

Язык: Английский

Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach DOI
Ravneet Kaur, Ravi P. Singh

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(15), С. 10325 - 10338

Опубликована: Июль 17, 2023

[1,2]-Phospha-Brook rearrangement entails the generation of α-oxygenated carbanions via umpolung process. Recently, these anionic species have been widely utilized for several C–C bond forming strategies, providing various useful frameworks that are difficult to access through conventional approaches. However, application this powerful methodology in development chiral strategies is still at nascent stage due challenges involved controlling chemoselectivity and enantioselectivity. This synopsis provides a detailed summary diastereo- and/or enantioselective chemical transformations using [1,2]-phospha-Brook rearrangement.

Язык: Английский

Процитировано

17

Asymmetric Synthesis of Trisubstituted Vicinal Diols through Copper(I)‐Catalyzed Diastereoselective and Enantioselective Allylation of Ketones with Siloxypropadienes DOI
Nan Jiang,

Pei‐Zhi Liu,

Zhi‐Zhou Pan

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Фев. 27, 2024

Chiral trisubstituted vicinal diols are a type of important organic compounds, serving as both common structure units in bioactive natural products and chiral auxiliaries asymmetric synthesis. Herein, by using siloxypropadienes the precursors allyl copper(I) species, copper(I)-catalyzed diastereoselective enantioselective reductive allylation ketones was achieved, providing syn-diols anti-diols good to excellent enantioselectivity. DFT calculations show that cis-γ-siloxy-allyl copper species generated favorably with either 1-TBSO-propadiene or 1-TIPSO-propadiene. Moreover, steric difference TBS group TIPS distinguishes face selectivity acetophenone, leading syn-selectivity for anti-selectivity Easy transformations were performed, demonstrating synthetic utility present method. one diol prepared above used suitable organocatalyst catalytic self-coupling aldimines situ B

Язык: Английский

Процитировано

8

Chiral Lewis Acid-Catalyzed Asymmetric Multicomponent Michael Reaction through [1,2]-Phospha-Brook Rearrangement DOI
Qianchi Lin, Siyuan Wang,

Rui Weng

и другие.

Organic Letters, Год журнала: 2023, Номер 25(34), С. 6262 - 6266

Опубликована: Авг. 21, 2023

The multicomponent catalytic asymmetric Pudovik addition/[1,2]-phospha-Brook rearrangement/Michael reaction sequence of isatins, phosphites, and 4-oxobutenoates was realized. A series oxindole derivatives containing two contiguous stereocenters obtained in high yields excellent stereoselectivities (up to >99% yield, >95:5 dr, ee) using a chiral Lewis acid catalyst. possible model is presented illustrate the stereocontrol.

Язык: Английский

Процитировано

14

Umpolung Phosphorylation of Tyrosine via 1,2-Phospha-Brook Rearrangement DOI

T Fukuta,

Toshifumi Tatsumi,

Kohei Fujiyoshi

и другие.

Organic Letters, Год журнала: 2024, Номер 26(41), С. 8827 - 8831

Опубликована: Окт. 10, 2024

Phosphorylated tyrosine is a fundamental building block of bioactive peptides and proteins. However, the chemoselective phosphorylation over other nucleophilic amino acid residues in unprotected remains significant challenge. Here we report an umpolung strategy that converts C-terminal into electrophilic spirolactone cyclohexadienone motif through hypervalent iodine oxidation, followed by 1,2-phospha-Brook rearrangement using phosphite diesters as phosphoryl donors. This reaction proceeds chemoselectively at phenol applicable to wide range peptide substrates containing various residues, including serine threonine.

Язык: Английский

Процитировано

5

Sequential In Situ-Formed Kukhtin–Ramirez Adduct and P(NMe2)3-Catalyzed O-Phosphination of α-Dicarbonyls with P(O)–H DOI
Yuan‐Yuan Huang, Nan Wang, Zheng‐Guang Wu

и другие.

Organic Letters, Год журнала: 2023, Номер 25(42), С. 7595 - 7600

Опубликована: Окт. 13, 2023

O-Phosphination of α-dicarbonyls via sequential in situ formation a Kukhtin-Ramirez adduct and P(NMe2)3-catalyzed process has been exploited for the synthesis α-phosphoryloxy carbonyls. A range P(O)-H derivatives, including diarylphosphine oxides, arylphosphinates, phosphinates, are competent candidates to be introduced into this transformation, various carbonyls obtained. This approach possesses advantages mild conditions, simple operations, atom economy, high efficiency, gram-scale synthesis, which make it promising toolbox.

Язык: Английский

Процитировано

10

Deciphering Asymmetric Brønsted Base-Aminocatalytic Mode in Pudovik/[1,2]-Phospha-Brook Rearrangement/Michael Cascade Reaction DOI
Ravneet Kaur,

Saurabh Singh Rautela,

M. M. Y. Ali

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(19), С. 14177 - 14182

Опубликована: Сен. 18, 2024

An approach involving the use of a bifunctional aminocatalyst containing Brønsted base and iminium activation sites for asymmetric multicomponent reactions [1,2]-phospha-Brook rearrangement has yet to be realized. Herein, we present an aminocatalytic enantioselective conjugate addition α-phosphonyloxy enolates formed

Язык: Английский

Процитировано

4

Stereoselective [1,2]-Phospha-Brook Rearrangement of CAMDOL-Derived H-Phosphonate: Synthesis of α-Trifluoromethyl Alcohols DOI
Ning Li, Qian Wu,

Yu Huang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

A highly efficient and stereoselective [1,2]-phospha-Brook rearrangement of fluoromethyl ketones has been achieved by utilizing a new type P-chiral H-phosphonate derived from CAMDOL, designated as CAMDOL-PHO. library 38 secondary alcohols featuring an α-trifluoromethyl or trifluoroaryl motif were afforded in up to 97% yield with 99:1 dr. Compared other known chiral auxiliaries, bicyclic CAMDOL exhibits superior induction ability due its unique center-chiral scaffold.

Язык: Английский

Процитировано

0

Catalytic Generation and Intermolecular Addition of Diarylmethyl Anions Utilizing [1,2]‐Phospha‐Brook Rearrangement Under Brønsted Base Catalysis DOI Creative Commons
Azusa Kondoh, Masahiro Terada

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(8), С. 1857 - 1862

Опубликована: Фев. 21, 2024

Abstract An intermolecular addition reaction involving an unconventional combination of a diarylmethyl anion and electrophile, which is mediated by the [1,2]‐phospha‐Brook rearrangement under Brønsted base catalysis, was developed. Diarylmethyl anions having benzofuran moiety were generated through with aid catalytic amount phosphazene P2‐ t Bu. The resulting carbanion intermediates trapped various electrophiles, such as α,β‐unsaturated ketones, aryl aldehydes, α‐ketoesters, N ‐Boc imines, providing corresponding diarylalkane derivatives in good yields.

Язык: Английский

Процитировано

3

Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H2O) DOI Creative Commons
Vladimir A. Kuimov, Svetlana F. Malysheva, Nataliya A. Belogorlova

и другие.

Molecules, Год журнала: 2025, Номер 30(6), С. 1367 - 1367

Опубликована: Март 18, 2025

It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in superbase suspension KOH/DMSO(H2O) at 85 °C 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates were earlier inaccessible a yield up 45%. The ESR data demonstrate unlike previously published phosphorylation elemental phosphorus, this new reaction proceeds via single electron transfer from polyphospide anions diaryl(hetaryl)ketones. This is example C-O-P bond generation during strongly basic media, which usually provides C-P formation.

Язык: Английский

Процитировано

0

Recent Developments in the [1,2]-Phospha-Brook Rearrangement Reaction DOI Open Access
Ning Li, Qian Wu,

Yu Huang

и другие.

International Journal of Molecular Sciences, Год журнала: 2025, Номер 26(7), С. 3065 - 3065

Опубликована: Март 27, 2025

The [1,2]-phospha-Brook rearrangement serves as a powerful synthetic strategy that enables efficient carbonyl umpolung through phosphoryl group migration, providing direct access to α-hydroxyphosphoryl compounds-a privileged class of synthons with broad applications in organophosphorus chemistry, medicinal and materials science. This review provides comprehensive overview recent progress methodologies, possible mechanisms, asymmetric transformations, highlighting key breakthroughs future directions this rapidly evolving field.

Язык: Английский

Процитировано

0