The Art and Science of Total Synthesis at the Dawn of the Twenty-First Century

Nicolaou, K. C.; Vourloumis, Dionisios; Winssinger, Nicolas; Baran, Phil S.

doi:10.1002/(sici)1521-3773(20000103)39:1<44::aid-anie44>3.3.co;2-c

Cited by 142 publications

(194 citation statements)

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“…P olyketide biosynthetic units are ubiquitous among natural products of diverse origin (1)(2)(3)(4)(5). Although the more common ones constitute hydroxy stereotriads originating from the condensation of propionyl-CoA biogenetic precursors (6), a small subgroup harbors deoxygenated motifs, commonly known as deoxypropionates.…”

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confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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The total synthesis of the marine cyclodepsipeptide (؊)-doliculide is described. An acyclic (2S,4S,6R)-trimethyl alkanoic acid precursor to the ''hydrocarbon'' portion of doliculide was synthesized starting with L-ascorbic acid based on a stereocontrolled iterative conjugate addition of lithium dimethylcuprate to acyclic ␦-Cmethyl ␣,␤-unsaturated ester derivatives. syn͞syn selectivity was achieved by relying on 1,3-induction in preferred folded conformations that avoid 1,5-syn-pentane interactions in the transition states. The nature of the ester moiety seems to play an important role in determining the syn͞anti ratios of C-methyl adducts. The 1-methyl-1-cyclopentyl ester group was found to confer the best syn selectivity to the cuprate addition products, especially in seven-carbon enoates.

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confidence: 99%

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Hanessian

Mascitti

Giroux

2004

Proc. Natl. Acad. Sci. U.S.A.

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“…As one of the most fundamental and important reactions in organic synthesis and chemical engineering, esterification has attracted considerable attention in recent years (Nicolaou et al, 2000;Xu and Xue, 2006). The most common method for preparing esters is to heat a carboxylic acid (R-COOH) with an alcohol (R'-OH) while removing the water that is formed.…”

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confidence: 99%

Esterification process to synthesize isopropyl chloroacetate catalyzed by lanthanum dodecyl sulfate

Zhang

Yin

et al. 2011

Braz. J. Chem. Eng.

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-Isopropyl chloroacetate has been synthesized by esterification of chloroacetic acid and isopropanol, using lanthanum dodecyl sulfate (LDDS) as the catalyst. Various factors that affected the esterification have been investigated, such as reaction time, different water-carrying agent and the amount of catalyst. Under the condition of 1.2/1 molar ratio of isopropanol to chloroacetic acid, 1.0% catalyst (molar percent of chloroacetic acid), 2.5 h reaction time, 5 mL cyclohexane as water-carrying agent and reflux temperature, the esterification conversion of isopropyl chloroacetate reaches 98.3%. The catalytic activity of LDDS is almost equal to that of a Brønsted acid. LDDS, as one kind of water-tolerant Lewis acid, is an excellent catalyst compared to the traditional Lewis acid.

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“…Chemists developed this ability over time allowing the conversion of small molecules into larger and ever more complex molecular architectures. The understanding and mastering of the rules of what could be once called a handcraft allowed its conversion into an art, the 'art of total synthesis' with so impressive achievements that they can be pointed out as master-pieces 1 . This field induced the discovery of many new chemical transformations, the development of enantioselective synthesis being a striking example.…”

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Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

et al. 2014

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Access to C n (n44) symmetric cyclic concave molecules with a different function on each of their n subunits is an unmet challenge. The reason lies in the lack of a post-functionalization method whose site selectivity is sufficiently understood, predictable and modulable to access most functionalization patterns. Here we disclose a new site-directing rule for a debenzylation reaction on cyclodextrins that solves this problem and allows the unprecedented access to penta-and ultimately hexa-differentiations of such C 6 concave cycles. This achievement opens the access to objects with very high-density information.

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The Art and Science of Total Synthesis at the Dawn of the Twenty-First Century

Cited by 142 publications

References 0 publications

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Total synthesis of the cytotoxic cyclodepsipeptide (-)-doliculide: The “ester” effect in acyclic 1,3-induction of deoxypropionates

Esterification process to synthesize isopropyl chloroacetate catalyzed by lanthanum dodecyl sulfate

Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

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