Recent Developments in Enantioselective Domino Reactions. Part B: First Row Metal Catalysts

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(6), P. 768 - 819

Published: Jan. 17, 2023

This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from first row metals, such as zinc, iron, copper, scandium, nickel, cobalt, titanium, chromium and magnesium special case, published since beginning 2019. It illustrates how much a diversity these allow an impressive range novel highly many types to be achieved, providing one-pot access very complex functionalized molecules simple starting materials.

Language: Английский

---

Copper‐Catalyzed Regiodivergent Asymmetric Difunctionalization of Terminal Alkynes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: June 25, 2024

We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting (R)-DTBM-Segphos CuBr, could efficiently achieve 1,1-difunctionalization aryl alkynes, while ligand switching to (S,S)-Ph-BPE result in 1,2-difunctionalization exclusively. In addition, alkyl substituted especially industrially relevant acetylene propyne, were also valid feedstocks for 1,1-difunctionalization. This protocol is characterized by good functional group tolerance, broad scope substrates (>150 examples), mild reaction conditions. showcase value this method late-stage functionalization complicated bioactive molecules simplifying synthetic routes toward key intermediacy natural product (bruguierol A). Mechanistic studies combined with DFT calculations provide insight into mechanism origins ligand-controlled regio- stereoselectivity.

Language: Английский

---

Enantioselective Synthesis of Secondary Homoallyl Borons by Copper-Catalyzed 1,1-Borylallylation of Terminal Alkynes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12102 - 12109

Published: July 30, 2024

The development of a single catalyst system that enables cascade reaction processes involving multiple components to occur in highly chemo-, regio-, and enantioselective manner presents significant challenge catalysis. Here, we introduce direct catalytic asymmetric synthesis enantioenriched secondary homoallyl borons by assembling four readily available components─terminal alkynes, boron reagents (HBdan), silyl hydrides (PMHS), allyl electrophiles─in hydroboration hydroallylation sequence. This complex assembly line is delicately controlled copper catalyst, effectively overcoming side reactions. features simple starting materials, mild conditions, structurally diverse products, high regio- enantioselectivities (up >20:1 r.r. 94% ee). utility the resulting products showcased through their versatile transformations further demonstrated formal total syntheses natural such as (−)-bruguierol A, (−)-enterolactone, (−)-antofine. Mechanistic studies were conducted illuminate operative pathway, key intermediates, crucial roles hydride source PMHS.

Language: Английский

---

Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: April 4, 2022

Tetracoordinate boron species have emerged as radical precursors via deboronation by photo-induced single electron transfer (SET) pathway. These reactions usually produce an alkyl and boron-bound species, the valuable are always discarded a by-product. Given importance of it will be very attractive if two parts could incorporated into eventual products. Herein we report photo-catalyzed strategy in which situ generated tetracoordinated decomposed both radicals under visible light irradiation, due to pre-installation vinyl group on aromatic ring, newly attacks while leaving ipso-position, then part moiety safely final product. Tertiary borons, secondary gem-diborons well 1,2-diborons, versatile electrophiles all tolerated this transformation, note, ortho-, meta- para-bromostyrenes demonstrated good capabilities. The reaction portraits high atom economy, broad substrate scope, diversified products with tertiary or quaternary carbon center generated, diborons substrates, Csp2-B Csp3-B established simultaneously, precious synthetic building blocks chemical synthesis.

Language: Английский

---

Photoredox-catalyzed stereo- and regioselective vicinal fluorosulfonyl-borylation of unsaturated hydrocarbons

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13893 - 13901

Published: Jan. 1, 2023

There has been considerable research on sulfur(vi) fluoride exchange (SuFEx) chemistry, which is considered to be a next-generation click reaction, and relies the unique balance between reactivity stability inherent in high valent organosulfur. The synthetic versatility of bifunctional handles containing fluorosulfonyl group presents great value opportunity for drug discovery. However, direct photoredox-catalyzed fluorosulfonyl-borylation process remains unexplored challenging due its system incompatibility limited strategies. Herein, we developed sequential photocatalytic radical difunctionalization strategy highly efficient stereoselective synthesis vicinal borides (VFSBs) with an integrated redox-active SO2F reagent. VFSBs acted as orthogonal synthons, were subjected range convenient transformations via cleavage C-B S(vi)-F bonds, including halogenation, Suzuki coupling, hydrogenation, SuFEX demonstrated potential VFSB moieties use skeleton linkage modification.

Language: Английский

---