1397699-75-0

Basic information

• Product Name: (S,E)-1-methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene
• Synonyms: (S,E)-1-methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene
• CAS NO: 1397699-75-0
• Molecular Weight: 300.422
• Mol File: 1397699-75-0.mol

Chemical Properties

• CAS DataBase Reference: (S,E)-1-methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene(CAS DataBase Reference)
• NIST Chemistry Reference: (S,E)-1-methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene(1397699-75-0)
• EPA Substance Registry System: (S,E)-1-methyl-4-((1-phenylpent-1-en-3-yl)sulfonyl)benzene(1397699-75-0)

Safety Data

• Hazardous Substances Data: 1397699-75-0(Hazardous Substances Data)

Upstream product

• 536-57-2 p-toluene sulfinic acid 
• 1608-27-1 ((1E)-penta-1,3-dien-1-yl)benzene 
• 3909-96-4 (1E,3E)-1-phenyl-1,3-pentadiene 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 824-79-3 sodium 4-methylbenzenesulfinate 

Relevant articles and documents

Palladium-Catalyzed Regio- A nd Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity

Chiral sulfones are important structural motifs in organic synthesis because of their widespread use in pharmaceutical chemistry. In particular, chiral allylic sulfones have drawn particular interest because of their synthetic utility. However, enantioselective synthesis of 1,3-disubstituted unsymmetrical chiral allylic sulfones remains a challenge. In this article, we report a protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- A nd enantioselective hydrosulfonylation of 1,3-dienes with sulfinic acids, which provides atom- A nd step-economical access to 1,3-disubstituted chiral allylic sulfones. The reaction occurs under mild conditions and has a broad substrate scope. Combined experimental and computational studies suggest that the reaction is initiated by a ligand-to-ligand hydrogen transfer followed by a C-S bond reductive elimination via a six-membered transition state. Steric repulsion between the olefinic C-H of the substrate and the tert-butyl group of (R)-DTBM-Segphos was found to be a key factor in the enantiocontrol.

Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step.

Direct substitution of primary allylic amines with sulfinate salts

The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 mol % 1,4- bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.