A safe and efficient method for conversion of 1,2- and 1,3-diols to cyclic carbonates utilizing triphosgene

Burk, Robert M.; Roof, Michael B.

doi:10.1016/0040-4039(93)85085-b

Cited by 146 publications

(85 citation statements)

References 13 publications

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“…In addition to its electron-withdrawing power and the reduced tendency for belimination, the cyclic carbonate ensures the conservation of the configuration at the OH-substituted C-atoms. Thus, the acetate function of diol 3 was first hydrolyzed yielding triol 17 which then was treated with triphosgene (CO(OCCl 3 )) following a procedure described by Burk and Roof [11] (Scheme 4). The configuration of triol 17 only allowed for the introduction of the cyclic carbonate moiety at the cis-oriented OH groups, thereby rendering further protective groups unnecessary.…”

Section: Methodsmentioning

confidence: 99%

Enantiospecific Total Synthesis of (−)-D-Noviose

Pankau

Kreiser

1998

HCA

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Section: Methodsmentioning

confidence: 99%

Enantiospecific Total Synthesis of (−)-D-Noviose

Pankau

Kreiser

1998

HCA

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“…Unfortunately, till today, the most convenient method for the synthesis of these products is the aminolysis of chloroformate, which is produced from phosgene and alcohols. 9,10 Although it is a versatile technique for carbamate synthesis, the toxicity and corrosion properties of phosgene and hydrogen chloride have caused severe environmental problems. 11 In the last decades, great efforts have been made in order to explore an environmentally benign method for carbamate synthesis.…”

Section: Introductionmentioning

confidence: 99%

Atom‐economy Synthesis of N‐Substituted Carbamate from Urea Derivative and Dimethyl Carbonate Catalyzed by La/SiO₂: Characterization and Activity

Guo

Shang

et al. 2010

Chin. J. Chem.

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A series of silica gel immobilized lanthanum catalysts were prepared for the atom-economy synthesis of N-substituted carbamates from urea derivatives and dimethyl carbonate. The La/SiO 2 catalysts with lanthanum loadings varied from 1.3 wt% to 8.5 wt% were characterized by AES, BET, XRD, TEM, FT-IR, XPS and TPD. According to the characterization, lanthanum species with particle sizes of 5-10 nm on the surface of silica gel were formed. The catalysts were all amorphous and the surface areas were 336.5-530.2 m 2 /g. NH 3 -TPD analysis showed that all samples exhibited similar acid strength with different acid amounts. FT-IR measurement indicated that the component of lanthanum species on the catalyst surface were La(OH) 3 , LaOOH and hydrated La 2 O 3 . Also, the peak value of the absolute amount of LaOOH was obtained with 4.3 wt% lanthanum loading. The BET surface area decreased dramatically when the lanthanum loading was above 4.3 wt%. In consideration of the results obtained from the catalytic reactions, it could be concluded that LaOOH was the possible active species and high surface area was important for the high catalytic activity.

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“…Considerable efforts were undertaken to effect the desired oxidative cleavage of 2.38; however, the formation of 2.39 was never observed. 26 Thus, despite the excitement of having circumvented the problems associated with the key Fischer indolization in this particular synthetic approach to picrinine (2.1), further modification of our synthetic plan would be required in order to access the natural product.…”

Section: 33mentioning

confidence: 99%

“…First, chemo-and diastereoselective Upjohn dihydroxylation 25 of the trans-hydrindenone 3.5, followed by protection of the resultant diol as the cyclic carbonate, 26 gave tetracyclic intermediate 3.28 in 78% yield over 2 steps. The success of this sequence validated our hypothesis shown in Figure 3.2 and allowed us to attempt the key Fischer indolization step.…”

Section: Earlier Oxidation Successful Fischer Indolization and Latementioning

confidence: 99%

Total Synthesis of (±)-Picrinine

2014

Synfacts

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Throughout history, organisms have ensured their survival by producing a wide variety of small molecule natural products. These entities commonly serve roles in cell function and signaling, and have also provided a defense system to combat infectious parasites. In the realm of synthetic chemistry, natural products serve as an architectural inspiration for the development of novel chemical transformations and molecular cascade processes. Ultimately, the synthesis of natural products that have biological importance holds promise toward the understanding of a plethora of biochemical pathways and the treatment of disease.iii This dissertation describes synthetic efforts toward the alkaloid picrinine. This molecule is a member of the akuammiline alkaloid class, and it bears a complex molecular scaffold unaddressed by synthetic chemistry. Central to the synthetic approach is the use of the Fischer indolization reaction as a platform for rapidly building molecular complexity and constructing the salient furanoindoline core of picrinine. The earlier part of this dissertation describes a firstgeneration approach to the synthesis of picrinine, while the ensuing chapter concerns a secondgeneration route, which resulted in its total synthesis. This dissertation's final section concerns the development of a unified and enantioselective approach to the akuammiline alkaloid family, in addition to a formal enantioselective synthesis of both aspidophylline A and picrinine. In summary, the synthetic endeavors described emphasize the importance natural products hold for the development of novel synthetic strategies and transformations.iv The dissertation of Joel Michael Smith is approved.

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A safe and efficient method for conversion of 1,2- and 1,3-diols to cyclic carbonates utilizing triphosgene

Cited by 146 publications

References 13 publications

Enantiospecific Total Synthesis of (−)-D-Noviose

Enantiospecific Total Synthesis of (−)-D-Noviose

Atom‐economy Synthesis of N‐Substituted Carbamate from Urea Derivative and Dimethyl Carbonate Catalyzed by La/SiO₂: Characterization and Activity

Total Synthesis of (±)-Picrinine

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A safe and efficient method for conversion of 1,2- and 1,3-diols to cyclic carbonates utilizing triphosgene

Cited by 146 publications

References 13 publications

Enantiospecific Total Synthesis of (−)-D-Noviose

Enantiospecific Total Synthesis of (−)-D-Noviose

Atom‐economy Synthesis of N‐Substituted Carbamate from Urea Derivative and Dimethyl Carbonate Catalyzed by La/SiO2: Characterization and Activity

Total Synthesis of (±)-Picrinine

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Atom‐economy Synthesis of N‐Substituted Carbamate from Urea Derivative and Dimethyl Carbonate Catalyzed by La/SiO₂: Characterization and Activity