ChemInform Abstract: A Mild, Palladium‐Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies.

Bissember, Alex C.; Levina, Anna; Fu, Gregory C.

doi:10.1002/chin.201309045

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“…Catalytic stereo-retentive cross-metathesis of 13 and commercially available 14 with Ru catechothiolate complex Ru-1 30 (9.0 mol %) delivered primary alcohol 15 in 77% yield (>98:2 Z/Z:Z/E). The ensuing conversion to the primary bromide and elimination of HBr was catalyzed by a phosphine-Pd complex, as outlined by Fu,31 affording mycothiazole in 56% overall yield (Scheme 9b). The above route allowed us to obtain 0.25 g of the natural product.…”

Section: A Concise Protecting Group-free and Enantioselective Synthesis Of Mycothiazolementioning

confidence: 99%

A Catalytic Approach for Enantioselective Synthesis of Homoallylic Alcohols Bearing a Z-Alkenyl Chloride or Trifluoromethyl Group. A Concise and Protecting Group-Free Synthesis of Mycothiazole

et al. 2019

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A protecting group-free strategy is presented for diastereo-and enantioselective routes that can be used to prepare a wide variety of Z-homoallylic alcohols with significantly higher efficiency than is otherwise feasible. The approach entails the merger of several catalytic processes and is expected to facilitate the preparation of a wide range of bioactive organic molecules. More specifically, Z-Chloro-substituted allylic pinacolatoboronate is first obtained through stereoretentive cross-metathesis between Z-crotyl-B(pin) (pin = pinacolato) and Z-dichloroethene, both of which are commercially available. The organoboron compound may then be used in the central transformation of the entire approach, namely, an α-, and enantioselective addition to an aldehyde, catalyzed by a proton-activated, chiral aminophenol-boryl catalyst. Catalytic crosscoupling can then furnish the desired Z-homoallylic alcohol in high enantiomeric purity. The olefin metathesis step can be carried out with substrates and a Mo-based complex that can be purchased. The aminophenol compound that is needed for the second catalytic step can be prepared in multi-gram quantities from inexpensive starting materials. A significant assortment of homoallylic alcohols bearing a Z-F 3 C-substituted alkene can be prepared with similarly high efficiency and regio-, diastereo-, and enantioselectivity. What is more, trisubstituted Z-alkenyl chloride moiety can also be accessed with similar efficiency albeit with somewhat lower αselectivity and enantioselectivity. The general utility of the approach is underscored by a succinct and protecting group-free, and enantioselective total synthesis of mycothiazole, a naturally occurring anticancer agent through a sequence that contains a longest linear sequence of nine steps (12 steps total), seven of which are catalytic, and generates mycothiazole in 14.5% overall yield.

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Section: A Concise Protecting Group-free and Enantioselective Synthesis Of Mycothiazolementioning

confidence: 99%

A Catalytic Approach for Enantioselective Synthesis of Homoallylic Alcohols Bearing a Z-Alkenyl Chloride or Trifluoromethyl Group. A Concise and Protecting Group-Free Synthesis of Mycothiazole

et al. 2019

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ChemInform Abstract: A Mild, Palladium‐Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies.

Abstract: The elimination from functionalized aliphatic organic halides is studied in the presence of base and a Pd‐phosphine catalyst.

Cited by 1 publication

References 1 publication

A Catalytic Approach for Enantioselective Synthesis of Homoallylic Alcohols Bearing a Z-Alkenyl Chloride or Trifluoromethyl Group. A Concise and Protecting Group-Free Synthesis of Mycothiazole

A Catalytic Approach for Enantioselective Synthesis of Homoallylic Alcohols Bearing a Z-Alkenyl Chloride or Trifluoromethyl Group. A Concise and Protecting Group-Free Synthesis of Mycothiazole

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