Catalytic Asymmetric Vinylogous Mukaiyama-Aldol (CAVM) Reactions:  The Enolate Activation

Bluet, Guillaume; Campagne, Jean‐Marc

doi:10.1021/jo015567s

Cited by 80 publications

(34 citation statements)

References 51 publications

(32 reference statements)

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“…Bluet and Campagne [78] described catalytic asymmetric vinylogous Mukaiyama reactions using different enolate activators, such as CuF·(S)-tolbinap, and various chiral nonracemic ammonium fluorides derived from cinchona alkaloids [Eq. (18)].…”

Section: Aldol and Mannich Reactionsmentioning

confidence: 99%

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

492

273

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There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

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Section: Aldol and Mannich Reactionsmentioning

confidence: 99%

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

492

273

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“…The use of the Carreira catalyst (S)-Tolbinap·CuF 2 produces a metallodienolate that provides exclusive g-site selectivity along with high yields and moderate enantioselectivities for the vinylogous aldol addition of dienol ether 62 to aromatic and aliphatic aldehydes (Scheme 25). [42] However, in the addition to cinnamaldehyde a 1:1 mixture of the vinylogous aldol adduct and the 1,4-addition product was obtained. Chemical degradation of 63 to a previously described enantiomerically pure compound and comparison of the optical rotation showed that the major enantiomer is the aldol adduct derived from Si-face attack on the aldehyde.…”

Section: Asymmetric Catalysismentioning

confidence: 99%

Catalytic, Enantioselective, Vinylogous Aldol Reactions

Denmark¹,

Heemstra²,

Beutner³

2005

Angew Chem Int Ed

444

149

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In 1935, R. C. Fuson formulated the principle of vinylogy to explain how the influence of a functional group may be felt at a distant point in the molecule when this position is connected by conjugated double-bond linkages to the group. In polar reactions, this concept allows the extension of the electrophilic or nucleophilic character of a functional group through the pi system of a carbon-carbon double bond. This vinylogous extension has been applied to the aldol reaction by employing "extended" dienol ethers derived from gamma-enolizable alpha,beta-unsaturated carbonyl compounds. Since 1994, several methods for the catalytic, enantioselective, vinylogous aldol reaction have appeared, with which varying degrees of regio- (site), enantio-, and diastereoselectivity can be attained. In this Review, the current scope and limitations of this transformation, as well as its application in natural product synthesis, are discussed.

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“…To start with the addition of g-dienolates to aldehydes, the so-called vinylogous Mukaiyama aldol reaction, Campagne et al studied the applicability of different types of catalyst when using the silyldienolate 115 as nucleophile [121]. In general, many products obtained by means of this type of reaction are of interest in the total synthesis of natural products.…”

Section: Modified Aldol Reactions -Vinylogous Aldol Nitroaldol and mentioning

confidence: 99%

“…In general, many products obtained by means of this type of reaction are of interest in the total synthesis of natural products. Although different types of alkaloid-based catalyst were used, enantioselectivity remained low -30% ee or below [121]. With regard to the type of organocatalyst investigated, Campagne et al focused on alkaloid-based phase-transfer catalysts; fluoride was always used as counter-ion.…”

Section: Modified Aldol Reactions -Vinylogous Aldol Nitroaldol and mentioning

confidence: 99%

Nucleophilic Addition to CO Double Bonds

Berkessel

Gröger

2005

Asymmetric Organocatalysis

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H CN HO 97 %, 97 % ee (ref. 23) 83 %, >98 % ee (ref. 26) H CN HO 61 %, 91 % ee (ref. 23) H CN HO 76 %, 93 % ee (ref. 23) H 3 CO H CN HO 78 %, 96 % ee (ref. 23) H 3 C H CN HO H 3 C 95 %, 91 % ee (ref. 22) H CN HO H 3 CO 83 %, 97 % ee (ref. 23) H CN HO PhO 97 %, 92 % ee (ref. 23) 84 %, 95 % ee (ref. 26) H CN HO 85 %, 83 % ee (ref. 22) H 3 CO H CN HO 45 %, 84 % ee (ref. 23) OCH 3 H CN HO 90 %, 80 % ee (ref. 22) F 3 C H CN HO 50 %, 89 % ee (ref. 22) N H H 3 C O O H O 76 %, 93 % ee (ref. 22) Scheme 6.2 132 6 Nucleophilic Addition to CbO Double Bonds 1: 83 %, 97 % ee (R ) (ref. 23) 2: 89 %, 56 % ee (S ) (ref. 33) t-Bu H O 91 %, 66 % ee (ref. 33) i-Pr H O 83 %, 64 % ee (ref. 33) H O 98 %, 74 % ee (ref. 33) n-C 5 H 11 H O 93 %, 81 % ee (ref. 33)

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Catalytic Asymmetric Vinylogous Mukaiyama-Aldol (CAVM) Reactions: The Enolate Activation

Cited by 80 publications

References 51 publications

Nonlinear Effects in Asymmetric Catalysis

Nonlinear Effects in Asymmetric Catalysis

Catalytic, Enantioselective, Vinylogous Aldol Reactions

Nucleophilic Addition to CO Double Bonds

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