136199-49-0

Upstream product

• 1375958-77-2 3-phenylpropyl tert-butoxycarbonylsulfamate 
• 122-97-4 3-Phenyl-1-propanol 
• 1189-71-5 isocyanate de chlorosulfonyle 

Downstream Products

• 14440-98-3 N-(benzyloxycarbonyl)-DL-3-amino-3-phenylpropionic acid 
• 355145-65-2 2,2-dioxo-4-phenyl-2λ⁶-[1,2,3]oxathiazinane-3-carboxylic acid benzyl ester 
• 1340519-23-4 C₉H₁₀⁽²⁾HNO₃S 
• 1151967-81-5 (±)-4-deuterio-4-phenyltetrahydro-1,2,3-oxathiazine 2,2-dioxide 
• 355145-63-0 (+/-)-4-phenyl-tetrahydro-1,2,3-oxathiazine-2,2-dioxide 

Relevant academic research and scientific papers

Enantioselective intramolecular C-H amidation of sulfamate esters catalyzed by chiral dirhodium(II) carboxylates

The chiral dirhodium(II) carboxylate-catalyzed enantioselective intramolecular C-H amidation reaction of sulfamate esters via in situ generated iminoiodinanes is described. The use of dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh2(S-TFPTTL)4, as a catalyst and PhI(OAc)2 as an oxidant provides cyclic sulfamidates in up to 48% ee.

Efficient general method for sulfamoylation of a hydroxyl group

The application of N,N-dimethylacetamide or 1-methyl-2-pyrrolidone as solvent clearly accelerated the sulfamoylation reaction of a hydroxyl group compared with the solvents used so far. The target sulfamates were obtained in the highest yield without a base. It became clear that 2 equiv. of sulfamoyl chloride to the starting material was sufficient to complete the reaction. It was confirmed that this condition could be applied to extensive hydroxyl groups. (C) 2000 Elsevier Science Ltd.

Iron-Catalyzed Intramolecular Amination of Aliphatic C-H Bonds of Sulfamate Esters with High Reactivity and Chemoselectivity

It is challenging to develop simple and low cost catalytic systems while maintaining high reactivity and selectivity. An iron-catalyzed intramolecular C-H amination of sulfamate esters using simple and cheap ligands is reported with general substrate scope (31 examples, up to 95% yield). The addition of second ligand, bipyridine, is able to accelerate the reaction and increase the yield. The ready availability of these iron catalysts provides a promising approach to selective introduction of nitrogen into hydrocarbon feedstock.

GENERAL CATALYST FOR C-H FUNCTIONALIZATION

The invention provides novel manganese catalysts such as [Mn(tBuPc)], which are general for the amination of all types of C(sp3)-H bonds (aliphatic, allylic, propargylic, benzylic, ethereal), including strong 1o aliphatic

Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations

The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4) 2 (1, qpy = 2,2′:6′,2″:6″, 2′′′:6′′′,2′′′′- quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp3)-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp3)-H bonds of hydrocarbons but also the C(sp3)-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI=NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)]n+ (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2] 2+ (CNTs) and [Fe(qpy)(NTs)]2+ (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI=NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate C NTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.

N-(tert -butoxycarbonyl)- N -[(triethylenediammonium)sulfonyl]azanide: A convenient sulfamoylation reagent for alcohols

A convenient and efficient procedure is described for the sulfamoylation of alcohols using N-(tert-butoxycarbonyl)-N-[(triethylenediammonium)sulfonyl] azanide (1). The ambient temperature stable reagent 1 reacts with phenols as well as primary and secondary alcohols to give high to modest yields. The relative reaction rate of substrates was determined (primary > phenol > secondary ? tertiary). The reagent's utility as a selective sulfamoylation reagent with polyols is also demonstrated.

Iron-catalyzed intramolecular allylic C-H amination

A highly selective C-H amination reaction under iron catalysis has been developed. This novel system, which employs an inexpensive, nontoxic [Fe IIIPc] catalyst (typically used as an industrial ink additive), displays a strong preference for allylic C-H amination over aziridination and all other C-H bond types (i.e., allylic > benzylic > ethereal > 3° > 2° ? 1°). Moreover, in polyolefinic substrates, the site selectivity can be controlled by the electronic and steric character of the allylic C-H bond. Although this reaction is shown to proceed via a stepwise mechanism, the stereoretentive nature of C-H amination for 3° aliphatic C-H bonds suggests a very rapid radical rebound step.

Copper-catalyzed intramolecular C-H amination

The amino-functionalization of tertiary, secondary and benzylic C-H bonds of tethered carbamates and sulfamates by iodosobenzene is catalyzed by Cu I-diimine complexes in moderate to good yield. Employing homochiral imine-Cucatalysts affords oxazolidinones and oxathiazinanes with modest enantioselectivity.

Highly efficient, enantioselective syntheses of (S)-(+)- and (R)-(-)-dapoxetine starting with 3-phenyl-1-propanol

(Chemical Equation Presented) A highly efficient, enantioselective sequence has been developed for the synthesis of (S)- and (R)-dapoxetine. The pathways involve the intermediacy of the 6-membered-ring sulfamate esters 4, which were generated by Du Bois asymmetric C-Hamination reactions of the prochiral sulfamate 3, catalyzed by the chiral dirhodium(II) complexes. During the course of our research, the absolute configuration of the enantiomer of 4-pheny[1,2,3]oxathiazinane 2,2-dioxide (4r), prepared by the Du Bois asymmetric C-H amination reaction of 3 and the Rh2(S-nap)4 catalyst, is determined to be R and not S as was originally reported.