Chemoenzymatic Synthesis of Carbasugars (+)-Pericosines A−C from Diverse Aromatic cis-Dihydrodiol Precursors

Abstract

cis-Dihydrocatechols, derived from biological cis-dihydroxylation of methyl benzoate, iodobenzene and benzonitrile, using the microorganism Pseudomonas putida UV4, were converted into pericosines A, C, and B, respectively. This approach constitutes the shortest syntheses, to date, of these important natural products with densely packed functionalities.

Synthesis of Marine-Derived Carbasugar Pericosines

“…The sample of natural 3 originated from the same batch as the originally reported material [64], and the ratio estimated from the peak area was 43:57 (14% ee), with the (À) enantiomer in slight excess, showing perfect agreement with the value for natural 3 (14% ee) estimated in Stevenson's reports [99].…”

“…In 2010, Stevenson et al reported the synthesis of (þ)-pericosines AÀC from cis-dihydrocatechols 85 (Scheme 8), 100 (Scheme 11), and 91 (Scheme 10), respectively [99]. These starting materials are expensive since they could be prepared by the biological cis-dihydroxylation of methyl benzoate, iodobenzene, and benzonitrile, respectively, using the microorganism Pseudomonas putida (UV4, 39D) [99].…”

“…These starting materials are expensive since they could be prepared by the biological cis-dihydroxylation of methyl benzoate, iodobenzene, and benzonitrile, respectively, using the microorganism Pseudomonas putida (UV4, 39D) [99]. The reported synthetic approach was basically similar to Donohoe's synthesis described above [67].…”

“…The specific rotation ([a] D 25 À32.6) of the SCHEME 11 Synthesis of (þ)-pericosine B by Stevenson. [67,99]. Because the specific rotation of natural pericosine B (2) was reported to be [a] D þ22.3 (ca.…”

Stereodivergent synthesis of diastereoisomeric carba analogs of glycal‐derived vinyl epoxides: A new access to carbasugars

“…The synthetic strategies adopted to obtain carbapyranoses can be broadly classified as: (i) synthetic methods that use non carbohydrates as starting materials [4][5][6] and (ii) protocols that utilize carbohydrates as the precursors. 7,8 In this framework, the use of carbohydrates provides important advantages, over the other methods, in the preparation of their carbocyclic analogs mostly because the enantiomeric purity of the target carbasugars is generally guaranteed.…”