Direct Reductive Amination of Aldehydes and Ketones Using Phenylsilane:  Catalysis by Dibutyltin Dichloride

Apodaca, Richard; Xiao, Wei

doi:10.1021/ol015948s

Cited by 162 publications

(66 citation statements)

References 18 publications

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“…Further development in this area was later reported by Apodaca and Xiao [29] , who showed that such tin catalysts could be used for the direct reducing amination of aromatic amines with aldehydes and ketones (Scheme 13.13 ).…”

Section: Tin-based Catalysts 331mentioning

confidence: 99%

Hydrosilylation of Imines

Riant¹

2008

Modern Reduction Methods

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13 IntroductionThe fi rst examples of the production of chiral secondary alcohols and amines by the reduction of a carbonyl or imino group using a silane as a reducing agent and a transition metal catalyst was reported during the mid 1970s by Kagan [1] . Following this fi rst report, the literature showed a growing interest in the discovery of effi cient catalytic systems for the hydrosilylation of ketones and aldehydes, while imines only started to show signifi cant advances much later . One of the main reasons is that most of the effi cient catalytic systems for the reduction of ketones were rhodium -based catalysts that usually required activated silanes such as bisaryl silanes. While these systems were active under very mild conditions, they suffered from strong economic drawbacks due to the cost of the catalysts, relatively poor catalytic effi ciency compared to hydrogenation and the cost of the silanes. Imines being poorer substrates than aldehydes and ketones suffered even more from these limitations and were neglected as substrates for hydrosilylation reactions until more effi cient systems were discovered during the 1990s. Indeed, imines are less electrophilic substrates compared to their carbonyl counterparts and are also susceptible to isomerization to enamines , when they posses one or more α -hydrogen. It is, however, possible to increase the electrophilic character of the imino group by the introduction of an aryl or an electron -withdrawing group on the nitrogen. The most common activating groups are tosyl, Boc or diphenylphosphinoyl. However, it is usually considered that only diphenylphosphinoyl combines ease of synthesis, stability to moisture and simplicity of removal for further transformations in synthesis. When designing a chiral catalyst for enantioselective addition of a nucleophile on an aldimine or a ketimine, another diffi culty arises from the possible cis -trans isomerization of the C = N double bond.However, nucleophilic addition to imines remains an attractive method for the synthesis of amines and increasing numbers of examples in the fi eld of asymmetric catalysis have been reported during the since the 1990s [2] . Concerning reduction processes, the costs of the catalytic systems and the silanes have often drawn chemists to develop more economic alternatives, such as hydrogenation.

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Section: Tin-based Catalysts 331mentioning

confidence: 99%

Hydrosilylation of Imines

Riant¹

2008

Modern Reduction Methods

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“…In contrast, organosilanes are mild and environmentally benign reducing agents, and in recent years, several reagent systems containing silanes such as Et 3 SiH/InCl 3 , [6] [7] PhSiH 3 / Bu 2 SnCl 2 , [8] PhSiH 3 /MoO 2 Cl 2 , [9] polymethylhydrosiloxane (PMHS)/TiA C H T U N G T R E N N U N G (O-i-Pr) 4 , [10] and polymethylhydrosil-A C H T U N G T R E N N U N G oxane (PMHS)/trifluoroacetic acid (TFA) [11] have also been employed in reductive amination.…”

Section: Introductionmentioning

confidence: 99%

Efficient and Highly Chemoselective Direct Reductive Amination of Aldehydes using the System Silane/Oxorhenium Complexes

Sousa¹,

Fernándes²

2010

Adv Synth Catal

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“…49.5, 37.4, 32.1, 29.6, 26.3, 22.9, 21.0, 14.3 3415, 2957, 2926, 2855, 1613, 1506, 1457, 1402, 1377, 1314, 1218, 1154, 1098, 816, 768, 724 cm 48.8, 37.8, 32.3, 29.9, 26.4, 23.2, 21.2, 14.5 3433, 29573433, , 29263433, , 28563433, , 16193433, , 15113433, , 14553433, , 13773433, , 13353433, , 12953433, , 12493433, , 11873433, , 11603433, , 10953433, , 1035aniline [16] 0, 137.6, 126.8, 111.3, 48.8, 37.1, 31.9, 29.4, 26.2, 22.8, 20.7, 14.3 3361, 29563361, , 29263361, , 28553361, , 15973361, , 15193361, , 15013361, , 14663361, , 13773361, , 12913361, , 12733361, , 11843361, , 11553361, , 1106aniline [17] 146.0, 144.9, 129.1, 128.9, 127.3, 126.0, 122.0, 114.6, 53.8, 25 3404, 3028, 2974, 2953, 2916, 2888, 2862, 1853, 1598, 1496, 1445, 1371, 1356, 1312, 1291, 1278, 1253, 1208, 1176, 1142, 1093, 1006, 947, 913, 809, 759, 145.6, 141.7, 128.8, 127.0, 126.1, 114.9, 114.8, 55.9, 54.5, 25.3 3376,3005,2982,2962,2920,2861,2836,1617,1504,1451,1368,1353,1302,…”

Section: General Procedures For the Zinc-catalyzed Hydroamination Reacmentioning

confidence: 99%

General Zinc‐Catalyzed Intermolecular Hydroamination of Terminal Alkynes

et al. 2008

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Catalytic hydroaminations are one of the most sustainable C-N bond-forming processes as a result of 100% atom economy and the availability of substrates. Here, it is shown that the intermolecular hydroamination of terminal alkynes with anilines proceeds smoothly in the presence of catalytic amounts of zinc triflate, an easily available and inexpensive zinc salt. Amination and subsequent reduction with NaBH3CN gives a variety of secondary and tertiary amines in up to 99% yield and with over 99% Markovnikov regioselectivity. Moreover, difficult functional groups such as nitro and cyano substituents are tolerated by the homogeneous catalyst.

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Direct Reductive Amination of Aldehydes and Ketones Using Phenylsilane: Catalysis by Dibutyltin Dichloride

Abstract: A procedure for direct reductive amination of aldehydes and ketones was developed which uses phenylsilane as a stoichiometric reductant and dibutyltin dichloride as a catalyst. Suitable amines included anilines and dialkylamines but not monoalkylamines.

Cited by 162 publications

References 18 publications

Hydrosilylation of Imines

Hydrosilylation of Imines

Efficient and Highly Chemoselective Direct Reductive Amination of Aldehydes using the System Silane/Oxorhenium Complexes

General Zinc‐Catalyzed Intermolecular Hydroamination of Terminal Alkynes

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