Catalytic Asymmetric Iodoesterification of Simple Alkenes

Abstract

Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide (di‐Zn) complex. For iodoesterification using p‐methoxybenzoic acid, the N‐iodonaphthalenimide (NIN)‐I2 system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo‐p‐methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π‐π stacking is harmonized on the single reaction sphere of di‐Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.

Recent developments in enantioselective zinc-catalyzed transformations

“…While asymmetric intramolecular halocyclizations have been well studied (Section 14), intermolecular versions using alkenes and carboxylic acids are still limited due to the difficulty of controlling the intermolecular reaction. In 2020, Arai et al described the first example of asymmetric iodoesterification of simple nonfunctionalized alkenes, which was catalyzed by a chiral zinc complex derived from (R)-BINOL-derived bis(aminoimino) ligand 380 (5 mol%) [161]. As shown in Scheme 126, the process employed N-iodonaphthalenimide 381 as iodide agent combined with I 2 .…”

Supramolecular Halogen Bonds in Asymmetric Catalysis

“…The Arai group has recently published a paper on an enantioselective haloesterfication reaction between styrenes 40 and benzoic acids 41 utilizing a chiral dinuclear zinc complex formed in situ from chiral ligand 42 and zinc carboxylate 43 ( Figure 12A; Arai et al, 2020). XBs were again used for the generation of active iodinating species.…”

Catalytic Asymmetric Chlorination of β-Ketoesters Using N-PFB-PyBidine-Zn(OAc)2

“…As part of a program for developing advanced halogenated compounds, a series of chiral metal catalysts for iodolactonization were developed [30][31][32][33]. Catalytic asymmetric iodolactonization was achieved using a newly developed chiral bis (imidazolidine) pyridine ligand (PyBidine)-metal complex [30].…”