Organocatalytic Trans Semireduction of Primary and Secondary Propiolamides: Substrate Scope and Mechanistic Studies
We report a chemoselective, phosphine‐catalyzed semireduction of primary and secondary propiolamides. In the presence of stoichiometric pinacolborane and catalytic n‐tributylphosphine, a variety of propiolamides were successfully converted to the corresponding acrylamides in excellent yield with (E)...
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| Veröffentlicht in: | Advanced synthesis & catalysis 2022-01, Vol.364 (1), p.172-178 |
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| container_title | Advanced synthesis & catalysis |
| container_volume | 364 |
| creator | Grams, R. Justin Lawal, Monsurat M. Szwetkowski, Connor Foster, Daniel Rosenblum, Carol Ann Slebodnick, Carla Welborn, Valerie Vaissier Santos, Webster L. |
| description | We report a chemoselective, phosphine‐catalyzed semireduction of primary and secondary propiolamides. In the presence of stoichiometric pinacolborane and catalytic n‐tributylphosphine, a variety of propiolamides were successfully converted to the corresponding acrylamides in excellent yield with (E)‐stereoselectivity. The reaction condition is tolerant of various functional groups including alkene, alkyne, ketone, or ester. Deuterium labeling studies established that the hydride from activated pinacolborane is added to the α‐carbon and the proton on the amide nitrogen is ed by the ß‐carbon to furnish the (E)‐acrylamides. DFT calculations revealed a clear energetic driving force for the (E)‐ over the (Z)‐isomer. |
| doi_str_mv | 10.1002/adsc.202101020 |
| format | Article |
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Justin ; Lawal, Monsurat M. ; Szwetkowski, Connor ; Foster, Daniel ; Rosenblum, Carol Ann ; Slebodnick, Carla ; Welborn, Valerie Vaissier ; Santos, Webster L.</creator><creatorcontrib>Grams, R. Justin ; Lawal, Monsurat M. ; Szwetkowski, Connor ; Foster, Daniel ; Rosenblum, Carol Ann ; Slebodnick, Carla ; Welborn, Valerie Vaissier ; Santos, Webster L.</creatorcontrib><description>We report a chemoselective, phosphine‐catalyzed semireduction of primary and secondary propiolamides. In the presence of stoichiometric pinacolborane and catalytic n‐tributylphosphine, a variety of propiolamides were successfully converted to the corresponding acrylamides in excellent yield with (E)‐stereoselectivity. The reaction condition is tolerant of various functional groups including alkene, alkyne, ketone, or ester. Deuterium labeling studies established that the hydride from activated pinacolborane is added to the α‐carbon and the proton on the amide nitrogen is ed by the ß‐carbon to furnish the (E)‐acrylamides. 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The reaction condition is tolerant of various functional groups including alkene, alkyne, ketone, or ester. Deuterium labeling studies established that the hydride from activated pinacolborane is added to the α‐carbon and the proton on the amide nitrogen is ed by the ß‐carbon to furnish the (E)‐acrylamides. DFT calculations revealed a clear energetic driving force for the (E)‐ over the (Z)‐isomer.</description><subject>Activated carbon</subject><subject>alkyne</subject><subject>Alkynes</subject><subject>boron</subject><subject>Catalytic converters</subject><subject>Deuterium</subject><subject>Functional groups</subject><subject>Ketones</subject><subject>organocatalysis</subject><subject>Phosphines</subject><subject>semireduction</subject><subject>stereoselective</subject><subject>Stereoselectivity</subject><subject>Substrates</subject><issn>1615-4150</issn><issn>1615-4169</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkElPwzAQhS0EEqVw5RyJc8vYieOEW1VWqaiVUs6W4wVcpXGwE6H-exKCypHTbN-b0TyErjHMMQC5FSrIOQGCAQOBEzTBKaazBKf56TGncI4uQtgBYJYxNkFh7d9F7aRoRXVorYy2XtQhKvTeeq062VpXR85EG2_3wh8iUat-KF2thmrjXWNdJfZW6XAXFV0ZWi9aHRXSNfoHftXyQ9Q2DLuLtlNWh0t0ZkQV9NVvnKK3x4ft8nm2Wj-9LBermYwxg5mmZSYlIzmUSqeUmkSnSsXU5IwaEsdGsVgJEkuRQNI3sDS5IQpkmeRMMhZP0c24t_Hus9Oh5TvX-bo_yUmKM4JpkuU9NR8p6V0IXhvejL9yDHwwlg_G8qOxvSAfBV-20od_aL64L5Z_2m_hvX6t</recordid><startdate>20220104</startdate><enddate>20220104</enddate><creator>Grams, R. 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Justin</creatorcontrib><creatorcontrib>Lawal, Monsurat M.</creatorcontrib><creatorcontrib>Szwetkowski, Connor</creatorcontrib><creatorcontrib>Foster, Daniel</creatorcontrib><creatorcontrib>Rosenblum, Carol Ann</creatorcontrib><creatorcontrib>Slebodnick, Carla</creatorcontrib><creatorcontrib>Welborn, Valerie Vaissier</creatorcontrib><creatorcontrib>Santos, Webster L.</creatorcontrib><collection>CrossRef</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Advanced synthesis & catalysis</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Grams, R. 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| language | eng |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Activated carbon alkyne Alkynes boron Catalytic converters Deuterium Functional groups Ketones organocatalysis Phosphines semireduction stereoselective Stereoselectivity Substrates |
| title | Organocatalytic Trans Semireduction of Primary and Secondary Propiolamides: Substrate Scope and Mechanistic Studies |
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