A Highly Efficient Gold‐Catalyzed Oxidative CC Coupling from CH Bonds Using Air as Oxidant

Xie, Jin; Li, Huamin; Zhou, Jiecong; Cheng, Yixiang; Zhu, Chengjian

doi:10.1002/ange.201107605

Cited by 62 publications

(25 citation statements)

References 70 publications

(13 reference statements)

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“…Despite significant progress, the promising oxidative CÀH/CÀH cross-coupling reactions which obviate the prefunctionalization of both coupling partners have been largely under developed. To the best of our knowledge, only the gold-catalyzed oxidative C(sp 2 ) À H/ C(sp 2 ) À H homocoupling, [6] C(sp 3 ) À H/C(sp 3 ) À H [7] cross-coupling, and C(sp 2 )ÀH/C(sp)ÀH cross-coupling [5] have been realized, and the C(sp 3 )ÀH/C(sp)ÀH cross-coupling still remains unexplored. Following our work in C(sp 3 )ÀH functionalization, [8] we were interested in the gold-catalyzed direct C(sp 3 )ÀH alkynylation.…”

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confidence: 99%

Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Zhang

Yang

et al. 2014

Angewandte Chemie

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In sharp contrast to the gold-catalyzed reactions of alkynes/allenes with nucleophiles, gold-catalyzed oxidative cross-couplings and especially CÀH/CÀH cross-coupling have been under represented. By taking advantage of the unique redox property and carbophilic p acidity of gold, this work realizes the first gold-catalyzed direct C(sp 3 ) À H alkynylation of 1,3-dicarbonyl compounds with terminal alkynes under mild reaction conditions, with subsequent cyclization and in situ oxidative alkynylation. A variety of terminal alkynes including aryl, heteroaryl, alkenyl, alkynyl, alkyl, and cyclopropyl alkynes all successfully participate in the domino reaction. The protocol offers a simple and region-defined approach to 3-alkynyl polysubstituted furans.

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Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Zhang

Yang

et al. 2014

Angewandte Chemie

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“…However, the pre- 20 functionalization of the starting materials in this protocol limited its application. More recently, combination of selective, catalytic activation of C-H bonds with functionalization to form C-S bonds has been a subject of particular interest in recent years.Various catalytic systems based on copper, 11 palladium, 12-15 ruthenium [16][17][18][19][20][21][22][23][24][25] 19 and rhodium 17- …”

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Gold nanoparticle catalyzed intramolecular C–S bond formation/C–H bond functionalization/cyclization cascades

et al. 2015

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The direct oxidative cross-dehydrogenative coupling (CDC) of two C À H bonds can be an efficient and relatively clean strategy in organic synthesis. Among these reactions, the oxidation of tertiary amines to generate iminium intermediates, as pioneered by Murahashi et al, [7] Li et al [8] and others, [9][10][11] has received considerable attention. Among these reactions, the oxidation of tertiary amines to generate iminium intermediates, as pioneered by Murahashi et al, [7] Li et al [8] and others, [9][10][11] has received considerable attention.

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confidence: 99%

“…The desired products were obtained with good enantioselectivity, but in lower yields ( Table 2, entries 9 and 10). [8][9][10][11] In summary, we have developed an enantioselective, direct, oxidative cross-dehydrogenative coupling reaction of tertiary amines with aldehydes. Prolonging the reaction time only slightly improved the reaction yields (largely as a result of the instability of 3 before reduction) and led to lower ee values because of product racemization (Table 2, entries 9-11).…”

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Enantioselective Oxidative Cross‐Dehydrogenative Coupling of Tertiary Amines to Aldehydes

et al. 2012

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The direct oxidative cross-dehydrogenative coupling (CDC) of two C À H bonds can be an efficient and relatively clean strategy in organic synthesis. [1] Various sp 3 CÀH bonds, such as benzylic and allylic CÀH bonds, [2,3] the a-CÀH bonds of amines and ethers, [4,5] and the CÀH bonds of alkanes [6] can be oxidized for direct reaction with carbon nucleophiles. Among these reactions, the oxidation of tertiary amines to generate iminium intermediates, as pioneered by Murahashi et al., [7] Li et al. [8] and others, [9][10][11] has received considerable attention. Carbonyl compounds, such as 1,3-dicarbonyls, [8e,f,h, 10b,g] a,bunsaturated ketones, [8f] and simple ketones [2c, 11] have been successfully coupled with tertiary amines by using metal catalysis, acid catalysis, metal/organic cooperative catalysis, or photoredox catalysis. In all of these reactions, the development of enantioselective catalysis remains a challenge. [12] Very recently, Wang and co-workers used metals together with chiral bisoxazoline ligands to realize enantioselective reactions of activated carbonyl nucleophiles (such as 1,3dicarbonyls and acetyl phosphates) to oxidatively generate iminiums or their analogues. [4d] However, this approach with chiral ligands was found to be unsuccessful for reactions starting with simple ketone nucleophiles, as reported by Klussmann and co-workers [11a] as well as Xie and Huang. [4c] Approaches that use asymmetric enamine catalysis [13] for the activation of carbonyl compounds have led to disappointing results (for example, less than 20 % ee) as well [4c, 11a,c,d] . As part of a larger program for developing sustainable oxidation chemistry, [14] we herein report an enantioselective oxidative coupling reaction of aldehydes and tertiary amines under cooperative amine and metal catalysis. The racemic version of this reaction was also realized by using metal catalysts alone (without amine catalysts), on account of its potential utility and the very different optimized conditions, relative to the enantioselective reactions.We examined metal-catalyzed oxidative coupling reactions between N-phenyltetrahydroisoquinoline (1 a) and pro-

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A Highly Efficient Gold‐Catalyzed Oxidative CC Coupling from CH Bonds Using Air as Oxidant

Cited by 62 publications

References 70 publications

Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Gold nanoparticle catalyzed intramolecular C–S bond formation/C–H bond functionalization/cyclization cascades

Enantioselective Oxidative Cross‐Dehydrogenative Coupling of Tertiary Amines to Aldehydes

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A Highly Efficient Gold‐Catalyzed Oxidative CC Coupling from CH Bonds Using Air as Oxidant

Cited by 62 publications

References 70 publications

Gold‐Catalyzed C(sp3)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Gold‐Catalyzed C(sp3)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Gold nanoparticle catalyzed intramolecular C–S bond formation/C–H bond functionalization/cyclization cascades

Enantioselective Oxidative Cross‐Dehydrogenative Coupling of Tertiary Amines to Aldehydes

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Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans

Gold‐Catalyzed C(sp³)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans