Intramolecular carbenoid ylide forming reactions of 2-diazo-3-keto-4-phthalimidocarboxylic esters derived from methionine and cysteine

Abstract

SummaryMethionine, S-benzylcysteine and S-allylcysteine were converted into 2-diazo-3-oxo-4-phthalimidocarboxylic esters 8a–c in three steps. Upon rhodium-catalysed dediazoniation, two intramolecular carbenoid reactions competed, namely the formation of a cyclic sulfonium ylide and that of a six-ring carbonyl ylide. The S-methyl and S-benzyl ylides 12a and b could be isolated, while S-allyl ylide 12c underwent a [2,3]-sigmatropic rearrangement. The short-lived carbonyl ylides derived from methionine and S-benzylcysteine formed head-to-tail dimers by a [3 + 3]-cycloaddition and could be trapped with external dipolarophiles, while the S-allyl derivative 14c yielded the pentacyclic compound 17 by an intramolecular [3 + 2]-cycloaddition reaction.

2,8-Diheterobicyclo[3.2.1]octane Ring Systems: Natural Occurrence, Synthesis and Properties

“…In more recent work, α-diazocarbonyl compounds derived from α-amino acids have been employed for various synthetic transformations 60 in the presence of either olefinic or acetylenic electron-withdrawing dipolarophiles. 61…”

Elucidating the mechanism and reactivity of the reaction between the donor–acceptor–acceptor 1,3-bisdiazo compound and cinnamyl alcohol catalyzed by Rh2(OAc)4: a DFT study

“…The outcomes, i.e. , active carbenoids, can participate in a variety of reactions, for example, cycloaddition, 6,7 ylide formation, 8,9 and X–H functionalization or insertion. 10,11 Among the various cycloadditions, the alkene cyclopropanation reaction is a classical one.…”

Catalytic Asymmetric Ring-Opening/Cyclopropanation of Cyclic Sulfur Ylides: Construction of Sulfur-Containing Spirocyclopropyloxindoles with Three Vicinal Stereocenters

“…For stabilized cyclic sulfur ylides or salts, 1- or 2-thianaphthalenes, , 10-thiaanthracene, and 9-thaphenanthrenes 1 – 3 can undergo not only thermal [1,2]- or [1,4]-rearrangement but also novel ring-opening reactions involving a rearrangement to construct organosulfur compounds (Scheme a). − The five- or six-membered cyclic sulfonium salts 4 are also employed as one-carbon synthons and sulfur sources to afford the sulfur-containing oxirane derivatives (Scheme b) . Recently, Maas has reported the conversion of methionine-derived diazoketones into the cyclic sulfonium ylides 5 – 7 in the presence of Rh 2 (OAc) 4 . The thiochiral center can be stabilized when the α-position was substituted by an ether group (Scheme c).…”

“…Of course, it cannot be ignored that the resulting products bear three vicinal stereocenters, and eight diastereoisomers exist in principle, making a great challenge to control the stereoselectivity. In addition, kinetic resolution or dynamic kinetic resolution of the cyclic sulfur ylides might exist. , Since the spirocyclopropanes have been reported to be capable of promoting the generation of the iPS cell and some sulfur-containing spirocyclic oxindoles have proven to be potential anticancer and antiproliferative agents, it is meaningful to investigate the reaction. Herein, we report our efforts in developing a chiral N , N ′-dioxide/Mg­(II) complex catalytic system to realize the ring-opening/cyclopropanation reaction of 1-alkyl-3-oxotetrahydro-1 H -thiophen-1-ium salts with ( E )-3-(oxyethylidene)-2-oxoindolines, constructing organosulfur spiro cyclopropyloxindoles with vicinal tertiary or quaternary carbon chiral centers in high efficiency.…”