Asymmetric Synthesis of α,α-Dibranched Amines by the Trimethylaluminum-Mediated 1,2-Addition of Organolithiums to <i>tert</i>-Butanesulfinyl Ketimines

Cogan, Derek A.; Ellman, Jonathan A.

doi:10.1021/ja983217q

Cited by 237 publications

(116 citation statements)

References 17 publications

(16 reference statements)

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“…We recently reported the first direct method for the asymmetric synthesis of a broad range of tertiary carbinamines by the unprecedented 1,2-addition of organolithium reagents to sulfinyl ketimines (eq. 4) [5,7]. Significantly, addition of Me 3 Al as a Lewis acid resulted in high yields (85 % average yield) and diastereoselectivities (89:11-99:1) for aryl and alkyl lithium additions to aliphatic and aromatic ketimine substrates.…”

Section: Asymmetric Synthesis Of Tertiary Carbinaminesmentioning

confidence: 97%

“…We developed the first direct condensation of sulfinamides with aldehydes and ketones to provide sulfinyl aldimines and ketimines, respectively [4,5]. The most straightforward method for the preparation of tert-butanesulfinyl aldimines is the condensation of aldehydes and tert-butanesulfinamide with CuSO 4 as a stoichiometric water scavenger and Lewis acid catalyst (eq.…”

Section: Preparation Of Tert-butanesulfinyl Iminesmentioning

confidence: 99%

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Applications of tert‐Butanesulfinamide in the Asymmetric Synthesis of Amines

Ellman

2003

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tert-Butanesulfinamide is prepared using catalytic enantioselective methods in two steps from the extremely inexpensive oil waste by-product, tert-butyl disulfide. Direct condensation of tert-butanesulfinamide with aldehydes and ketones provides tert-butanesulfinyl imines in uniformly high yields. The tert-butanesulfinyl group activates the imines for the addition of many different classes of nucleophiles, serves as a powerful chiral directing group, and after nucleophilic addition is readily cleaved by treatment with acid. A wide range of highly enantioenriched amines, including α-branched and α,α-dibranched amines, α-and β-amino acids, 1,2-and 1,3-amino alcohols and α-trifluoromethyl amines are efficiently synthesized using this methodology.

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Section: Asymmetric Synthesis Of Tertiary Carbinaminesmentioning

confidence: 97%

Section: Preparation Of Tert-butanesulfinyl Iminesmentioning

confidence: 99%

Applications of tert‐Butanesulfinamide in the Asymmetric Synthesis of Amines

Ellman

2003

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“…[10] However, these reaction conditions were not effective for the synthesis of ketimines 4 which were exclusively prepared under the influence of titanium tetraethoxide in refluxing THF. [10,11] More recently, new methods for the synthesis of N-tert-butanesulfinyl imines 3 through a condensation of aldehydes 2…”

Section: Introductionmentioning

confidence: 99%

One‐Pot Synthesis of N‐tert‐Butylsulfinylimines and Homoallylamine Derivatives from Epoxides

2016

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The reaction of epoxides with tert‐butanesulfinamide in the presence of a Lewis acid, such as erbium triflate or boron trifluoride–diethyl ether, in THF as solvent, under microwave or thermal activation, produces N‐tert‐butylsulfinylimines in reasonable yields. Aromatic and gem‐disubstituted and trisubstituted alkyl epoxides performed better than mono‐alkyl‐substituted compounds. After imine formation, a subsequent indium‐promoted allylation can be carried out in the same reaction flask in a single synthetic operation leading to homoallylamine derivatives with generally high yields.

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“…因该亚胺含有一个手性硫中心和一个潜在的手性碳原子, 而被广泛应用于不对称合成中. 该亚胺其碳氮双键经不对称加成后, 可以合成手性氨 [1] 、手性支链氨 [2,3] 、手性氨基酸 [4,5] 、手性氨基醇 [6,7] 、手性氨基酮 [8,9] 、手性氮杂环 [10] 等小分子化合物; 也可以参与手性生物大分子药物 [11～13] 的合成. 据报道水杨醛类亚胺是合成苯并呋喃 [14,15] 、苯并噁嗪 [16,17] 、苯并恶唑 [18] 等杂环的重要中间体, 其碳氮双键经不对称还原后形成的邻胺甲基苯酚 [19] 类化合物是手性金属催化剂的重要配体 [20,21] .…”

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Study on Synthesis ofortho-Hydroxyl AromaticN-tert-Butylsulfinyl Imines under Microwave Irradiation

赵云辉¹,

任新芳²,

刘汉文³

et al. 2014

Chin. J. Org. Chem.

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Chiral N-tert-butanesulfinyl imines have been shown to be important intermediates for asymmetric synthesis in recent years. Eleven new (R,E)-N-(2-hydroxybenzylidene)-tert-butyl-sulfinamides (3) were synthesized from salicylaldehydes 1 and chiral tert-butanesulfinamide 2 under microwave irradiation in moderate to good yields. The reaction could work well in the mixture of KHSO 4 /PhMe or Cs 2 CO 3 /CH 2 Cl 2 . And the results show that the KHSO 4 /PhMe reaction system is helpful for the salicylaldehydes with electron-donating group; however, the Cs 2 CO 3 /CH 2 Cl 2 reaction system is applicable to the salicylaldehydes with electron-deficient group and steric hindrance group. The structures of these new compounds were determined by 1 H NMR, 13 C NMR, IR and HRMS.

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Asymmetric Synthesis of α,α-Dibranched Amines by the Trimethylaluminum-Mediated 1,2-Addition of Organolithiums to tert-Butanesulfinyl Ketimines

Cited by 237 publications

References 17 publications

Applications of tert‐Butanesulfinamide in the Asymmetric Synthesis of Amines

Applications of tert‐Butanesulfinamide in the Asymmetric Synthesis of Amines

One‐Pot Synthesis of N‐tert‐Butylsulfinylimines and Homoallylamine Derivatives from Epoxides

Study on Synthesis ofortho-Hydroxyl AromaticN-tert-Butylsulfinyl Imines under Microwave Irradiation

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