cas 196929-78-9, (R)-(+)-2-Methyl-2-propanesulfinamide

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Improved synthesis of tert-butanesulfinamide suitable for large-scale production
(Matrix presented) An improved synthesis of tert-butanesulfinamide that overcomes the scalability problems of the previous syntheses is described. The key step is the catalytic asymmetric oxidation of the inexpensive di-tert-butyl disulfide starting material. The new homogeneous reaction conditions utilize an inexpensive chiral ligand prepared in a single step from commercially available cis-1-amino-indan-2-ol. The reaction is performed at a 2.3 M concentration in the practical solvent acetone and can readily be run on a kilogram scale.
Weix, Daniel J.,Ellman, Jonathan A.
p. 1317 - 1320
(2003)
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Catalytic asymmetric oxidation of tert-butyl disulfide. Synthesis of tert-butanesulfinamides, tert-butyl sulfoxides, and tert-butanesulfinimines
The first example of the catalytic asymmetric oxidation of tert-butyl disulfide (1) is described. The product, tert-butyl tert-butanethiosulfinate (2) is obtained with 91% enantiomeric excess in yields of ≤92% on scales as large as 1 mol. The application of H2O2 as stoichiometric oxidant in the presence of 0.25 mol% of VO(acac)2 and 0.26 mol% of a chiral Schiff base ligand, 6a, is both convenient and cost-effective. Thiosulfinate ester 2 is chemically and optically stable and serves as an excellent precursor to chiral tert-butanesulfinyl compounds by the stereospecific nucleophilic displacement of tert-butyl thiolate. Addition of LiNH2 in liquid ammonia and THF provides tert-butanesulfinamide (3; 91% yield). A single recrystallization provides enantiomerically pure 3 in 71-75% overall yield from disulfide 1. Enantiomerically pure thiosulfinate ester 2 also reacts readily and stereospecifically with Grignard reagents, organolithiums, lithium amides, and lithium imine salts to provide enantiomerically pure chiral sulfoxides, sulfinamides, and sulfinimines in good yield.
Cogan, Derek A.,Liu, Guangcheng,Kim, Kyungjin,Backes, Bradley J.,Ellman, Jonathan A.
p. 8011 - 8019
(1998)
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Method for preparing chiral tert-butyl sulfinamide
The invention belongs to the technical field of chemical synthesis, and provides a method for preparing (R)-tert-butyl sulfinamide. The method comprises the following steps: (1) preparing a Grignard compound by using halogenated tert-butane as an initial raw material through a Grignard reaction, introducing sulfur dioxide gas into the Grignard reaction solution, and reacting to obtain tert-butyl sulfinic acid; (2) converting tert-butyl sulfinic acid into tert-butyl sulfinyl chloride by adopting thionyl chloride; (3) converting tert-butyl sulfinyl chloride into tert-butyl sulfinate through an alcohol reagent and an alkaloid compound; and (4) converting tert-butyl sulfinate into chiral (R)-tert-butyl sulfinate amine in the presence of ferric nitrate, lithium metal or sodium metal. Accordingto the method, the defects of an existing process are overcome, foul tert-butyl mercaptan is not used, used halogenated tert-butane and the like are common and cheap materials, alkaloid compounds canbe recycled, and the method is more suitable for industrial production.
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Paragraph 0021; 0026-0027

(2021/01/30)

Method of synthesizing enantiomerically pure tert-butanesulfinamide
The invention discloses a method of synthesizing enantiomerically pure tert-butanesulfinamide. The method comprises the following steps of using tert-butyl disulfide and hydrogen peroxide for selective oxidation, then performing reaction on a product and an acylation reagent to obtain tert-butylsulfinyl chloride or tert-butylsulfinyl bromide, then performing reaction on the tert-butylsulfinyl chloride or the tert-butylsulfinyl bromide and hydrazine hydrate to obtain tert-butylsulfinyl hydrazine, then performing reaction on the tert-butylsulfinyl hydrazine and a DTTA resolving agent for resolution and dissociation, and performing zinc/acetic acid pyrolysis to obtain the enantiomerically pure tert-butanesulfinamide. The method provided by the invention is simple, convenient and stable in technological operation and high in yield, is environmentally friendly, is cheap and available in raw materials compared with the prior art, lowers the production cost of the existing enantiomerically pure tert-butanesulfinamide and is beneficial to industrialized mass production.
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Paragraph 0058-0059

(2018/09/11)

Method for preparing enantiomer pure methylpropane-2-sulfinamide
The invention discloses a method for preparing enantiomer pure methylpropane-2-sulfinamide. The method comprises the following steps: performing selective oxidation on tertiary butyl dithioether and hydrogen peroxide; adding an acylation reagent so as to obtain tertiary butyl sulfonyl chloride or tertiary butyl thionyl bromide; adding hydrazine hydrate so as to obtain tertiary butyl thionyl hydrazine; further performing resolving dissociation with a tartaric acid resolving agent; performing cracking with zinc acetate, thereby obtaining the enantiomer pure methylpropane-2-sulfinamide. The method is simple and stable in process operation, high in yield and good in environment protection, and compared with a conventional process, the method is low in raw material price, easy in raw material obtaining, capable of reducing the production cost of conventional enantiomer pure methylpropane-2-sulfinamide, and beneficial to industrial on-scale production.
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Paragraph 0015; 0058; 0059

(2018/09/29)

Method for preparing pure enantio-methylpropane-2-sulfinamide
The invention discloses a method for preparing pure enantio-methylpropane-2-sulfinamide. The method comprises the following steps: carrying out selective oxidation on di-tert-butyl disulfide and hydrogen peroxide, reacting with an acylation reagent so as to obtain tert-butylsulfinyl chloride and tertiary butyl sulfonyl bromide, further reacting with hydrazine hydrate so as to obtain tertiary butylhydrazide, further carrying out resolution and separation with a DBTA resolving agent, and carrying out cracking with zinc acetate, thereby obtaining the pure enantio-methylpropane-2-sulfinamide. Themethod is simple, convenient and stable in process operation, high in yield and good in environment protection, and compared with a conventional process, the method is cheap and easy in raw materialobtaining, low in production cost of pure enantio-methylpropane-2-sulfinamide, and beneficial to industrial on-scale production.
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Paragraph 0015; 0041; 0058; 0059

(2018/10/19)

Process for synthesizing chiral tert-butanesulfinyl amide
The invention discloses a process for synthesizing chiral tert-butanesulfinyl amide. The process includes carrying out reaction on tert-butyl mercaptan and iodine/hydrogen peroxide acetone to generate di-tert-butyl disulfide; oxidizing hydrogen peroxide under the catalytic effect of vanadium to generate chiral tert-butyl sulfenyl tert-butyl mercaptide; carrying out one-pot reaction on the chiral tert-butyl sulfenyl tert-butyl mercaptide and lithium reagents/liquid ammonia in the presence of alkyl chloride to obtain the tert-butanesulfinyl amide. Compared with existing processes, the process has the advantages that the smoothness of the process can be enhanced, the usage of the liquid ammonia can be reduced to a great extent, and the operational efficiency can be improved.
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Paragraph 0016; 0017; 0020; 0021

(2017/08/28)

NEW PROCESSES AND INTERMEDIATES USEFUL IN SYNTHESIS OF NEP INHIBITORS
The invention relates to a novel process, novel process steps and novel intermediates useful in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors such as sacubitril, and prodrugs thereof.
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Page/Page column 44

(2017/04/11)

HALOGEN-ALKYL-1,3 OXAZINES AS BACE1 AND/OR BACE2 INHIBITORS
The present invention provides compounds of formula (I) having BACE1 and/or BACE2 inhibitory activity, their manufacture, pharmaceutical compositions containing them and their use as therapeutically active substances. The active compounds of the present invention are useful in the therapeutic and/or prophylactic treatment of e.g. Alzheimer's disease and type 2 diabetes.
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(2014/04/03)

DMAP-Catalysed Sulfinylation of Diacetone- D -Glucose: Improved Method for the Synthesis of Enantiopure tert-Butyl Sulfoxides and tert-Butanesulfinamides
An improved method for the tert-butanesulfinylation of diacetone glucose with tert-butanesulfinyl chloride is reported. The method is based on a beneficial effect of catalytic DMAP, which enhances both the rate of the reaction and the enantioselectivity of the process to give (R S)-diastereomer 2 R S with a 94 % de and in quantitative yield. (R S)-DAG sulfinate ester 2 R S is an excellent intermediate for the synthesis of enantiopure tert-butyl sulfoxides. Grignard agents and organolithium reagents can displace smoothly the diacetone glucose moiety to give synthetically relevant enantiopure sulfoxides, including highly functionalized derivatives, in high yields and with high enantioselectivities. (R S)-DAG sulfinate ester 2 R S is also an excellent N-sulfinylating agent; simple addition of LiHMDS (lithium hexamethyldisilazide) in THF gives (S S)-tert-butanesulfinamide, and N-tert-butanesulfinylimines are then formed in a two-step one-pot manner. N-Alkylated tert-butanesulfinamides are formed by the condensation of 2 R S with lithium amides.
Chelouan, Ahmed,Recio, Rocío,Alcudia, Ana,Khiar, Noureddine,Fernández, Inmaculada
p. 6935 - 6944
(2016/02/19)

Design and synthesis of chiral oxathiozinone scaffolds: Efficient synthesis of hindered enantiopure sulfinamides and sulfinyl ketimines
Is that S-O? The title scaffolds have a highly active and properly differentiated S-O bond for the efficient synthesis of enantiopure sulfinamides. The method is practical, green, and has the potential to provide an economical commercial process for the synthesis of bulky sulfinamides. Copyright
Han, Zhengxu S.,Herbage, Melissa A.,Mangunuru, Hari P. R.,Xu, Yibo,Zhang, Li,Reeves, Jonathan T.,Sieber, Joshua D.,Li, Zhibin,Decroos, Philomen,Zhang, Yongda,Li, Guisheng,Li, Ning,Ma, Shengli,Grinberg, Nelu,Wang, Xiaojun,Goyal, Navneet,Krishnamurthy, Dhileep,Lu, Bruce,Song, Jinhua J.,Wang, Guijun,Senanayake, Chris H.
supporting information
p. 6713 - 6717
(2013/07/26)

Asymmetric synthesis of sulfinamides using (-)-quinine as chiral auxiliary
A process has been designed and demonstrated for the asymmetric synthesis of sulfinamides using quinine as auxiliary. A variety of chiral sulfinamides including N-alkyl sulfinamides with diverse structure were prepared in good yields and excellent enantioselectivity starting from easily available and inexpensive reagents. The auxiliary quinine could be recovered and recycled.
Zhang, Yongda,Chitale, Sampada,Goyal, Navneet,Li, Guisheng,Han, Zhengxu S.,Shen, Sherry,Ma, Shengli,Grinberg, Nelu,Lee, Heewon,Lu, Bruce Z.,Senanayake, Chris H.
experimental part
p. 690 - 695
(2012/02/16)

Enantioselective synthesis of diverse sulfinamides and sulfinylferrocenes from phenylglycine-derived chiral sulfinyl transfer agent
A new chiral sulfinyl transfer auxiliary derived from readily available phenylglycine was developed. This auxiliary is utilized to synthesize a diverse array of alkyl- and arylsulfinamides and sulfinylferrocenes in high yields and excellent ee's. The desired products are produced in a one-pot sequence from the oxathiazolidine 2-oxide by two sequential nucleophilic additions that proceed in a stereospecific manner.
Han, Zhengxu S.,Meyer, Angelica M.,Xu, Yibo,Zhang, Yongda,Busch, Robert,Shen, Sherry,Grinberg, Nelu,Lu, Bruce Z.,Krishnamurthy, Dhileep,Senanayake, Chris H.
supporting information; scheme or table
p. 5480 - 5484
(2011/08/09)

Chiral sulfur derivatives in the allylation of acyl hydrazones: C 2-symmetric bis-sulfinamides as enhanced chiral organic promoters.
Monosulfinamides and C2-symmetric bis-sulfinamides are convenient neutral chiral promoters in the allylation of acyl hydrazones, the nature of the spacer and the substituent at the sulfinyl sulfur are key elements for the enantioselectivity of the process.
Fernandez, Inmaculada,Alcudia, Ana,Gori, Beatrice,Valdivia, Victoria,Recio, Rocio,Garcia, Maria Victoria,Khiar, Noureddine
supporting information; experimental part
p. 4388 - 4393
(2010/10/20)

Recycling the tert-butanesulfinyl group in the synthesis of amines using tert-butanesulfinamide
A practical process for recycling the tert-butanesulfinyl group upon deprotection of N-tert-butanesulfinyl amines has been achieved. Treatment of N-tert-butanesulfinyl amines with HCl in cyclopentyl methyl ether results in complete conversion to tert-butanesulfinyl chloride and the corresponding amine hydrochloride salt, which is isolated by filtration in analytically pure form and in quantitative yield. Treatment of the resulting sulfinyl chloride solution with aqueous ammonia then provides analytically pure tert-butanesulfinamide in 97% yield. Alternatively, the tert-butanesulfinyl chloride solution can be treated with ethanol and catalytic quinidine as a sulfinyl transfer catalyst to provide a cyclopentyl methyl ether solution of ethyl tert-butanesulfinate with 88% ee. Addition of NaNH2 in ammonia followed by simple trituration of the product with octane provides tert-butanesulfinamide with 99% ee and in 67% overall isolated yield based upon the starting N-tert-butanesulfinyl amine.
Wakayama, Masakazu,Ellman, Jonathan A.
experimental part
p. 2646 - 2650
(2009/08/15)

(RS)-(+)-2-Methyl-2-propanesulfinamide: [Tert-butanesulfinamide]
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Weix, Daniel J.,Ellman, Jonathan A.,Wang, Xiao,Curran, Dennis P.
p. 157 - 165
(2017/09/30)

A method of manufacturing an amine stereoisomerically
This invention provides intermediates useful in a method of preparing amine stereoisomers. It also provides a method of preparing sulfoxide and sulfinylamine stereoisomers using certain of the intermediates.
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Page/Page column 56-57

(2010/02/12)

A rapid and general method for the asymmetric synthesis of 2-substituted pyrrolidines using tert-butanesulfinamide
A new method for the asymmetric synthesis of 2-substituted pyrrolidines in three steps from commercially available starting materials is described. Addition of the Grignard reagent prepared from 2-(2-bromoethyl)-1,3-dioxane to N-tert-butanesulfinyl aldimines proceeds in high yields and with good diastereoselectivities. The sulfinamide products are then cleanly converted into pyrrolidines in one step. The Royal Society of Chemistry 2005.
Brinner, Kristin M.,Ellman, Jonathan A.
p. 2109 - 2113
(2007/10/03)

Practical and highly stereoselective technology for preparation of enantiopure sulfoxides and sulfinamides utilizing activated and functionally differentiated N-sulfonyl-1,2,3-oxathiazolidine-2-oxide derivatives
A simple, general, and practical technology to prepare enantiopure 1,2,3-oxathiazolidine-2-oxide derivatives using chiral aryl N-sulfonyl aminoalcohol derivatives and thionyl chloride is reported. The versatility of these novel chiral building blocks (MIOO and TMPOO), was exemplified by the expedient production of a variety of unique chiral sulfoxides and valuable chiral sulfinamides in excellent yields and enantiopurities.
Han, Zhengxu,Krishnamurthy, Dhileepkumar,Grover, Paul,Fang, Q. Kevin,Su, Xiping,Wilkinson, H. Scott,Lu, Zhi-Hui,Magiera, Daniel,Senanayake, Chris H.
p. 6386 - 6408
(2007/10/03)

The Preparation of (1α,3β)-3-Hydroxycholestane-4,6-diene- 1,25-diol Diacetate from a 5,7-Diene Precursor: A New Method for the Synthesis of Heteroannular Dienes
Starting from the 7α-bromide 5a, a regioselective synthesis of (1α,3β)-3-hydroxycholestane-4,6-diene-1,25-diol diacetate (2) is described. The preparative removal of contaminating 5,7-diene 9 was accomplished by the formation of the corresponding Diels-Alder adduct 11. Acetylation of the diacetate 2 followed by acid-catalyzed elimination and rearrangement yielded styrene 13.
Arnum, Susan D. Van,Carpenter, Barry K.,Parrish, David R.,MacIntrye, Archibald
p. 8533 - 8536
(2007/10/03)

Development and application of a new general method for the asymmetric synthesis of syn- and anti-1,3-amino alcohols
A general method is described for asymmetric synthesis of both syn- and anti-1,3-amino alcohols. The first application of metalloenamines derived from N-sulfinyl imines is reported for the highly diastereoselective addition to aldehydes. The reduction of the product β-hydroxy N-sulfinyl imines 2 with catecholborane and LiBHEt3 provides syn- and anti-1,3-amino alcohols with very high diastereomeric ratios. This method was found to be effective for a variety of substrates incorporating either aromatic or various aliphatic substituents. The convergent and efficient asymmetric syntheses of the two natural products, (-)-8-epihalosaline and (-)-halosaline, were also accomplished.
Kochi, Takuya,Tang, Tony P.,Ellman, Jonathan A.
p. 11276 - 11282
(2007/10/03)

First application of tunable alkyl or aryl sulfinamides to the stereoselective synthesis of a chiral amine: asymmetric synthesis of (R)-didesmethylsibutramine ((R)-DDMS) using (R)-triethylmethylsulfinamide ((R)-TESA).
A highly diastereoselective addition of i-BuLi to a triethylmethylsulfinamide derived aldimine was used as the key step in the first asymmetric synthesis of (R)-didesmethylsibutramine, a metabolite of sibutramine for the potential treatment of CNS disorders. [reaction: see text]
Han, Zhengxu,Krishnamurthy, Dhileepkumar,Pflum, Derek,Grover, Paul,Wald, Stephen A,Senanayake, Chris H
p. 4025 - 4028
(2007/10/03)

Properly designed modular asymmetric synthesis for enantiopure sulfinamide auxiliaries from N-sulfonyl-1,2,3-oxathiazolidine-2-oxide agents
Simple and practical asymmetric synthesis of functionally differentiated aminoindanol based endo-N-sulfonyl 1,2,3-oxathiazolidine-2-oxide as sulfinyl transfer agents are developed. The importance of these new and unique sulfinyl transfer reagents are exemplified by the expedient production of several sulfinamide ligands, including either enantiomer of (R)-tert-butanesulfinamide in excellent yields and enantiopurities. Copyright
Han, Zhengxu,Krishnamurthy, Dhileepkumar,Grover, Paul,Fang, Q. Kevin,Senanayake, Chris H.
p. 7880 - 7881
(2007/10/03)

Catalytic asymmetric synthesis of tert-butanesulfinamide. Application to the asymmetric synthesis of amines
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Liu,Cogan,Ellman
p. 9913 - 9914
(2007/10/03)