{"id":9658,"date":"2016-02-05T17:59:29","date_gmt":"2016-02-05T22:59:29","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=9658"},"modified":"2025-02-28T12:19:36","modified_gmt":"2025-02-28T18:19:36","slug":"gilman-reagents-organocuprates-what-theyre-used-for","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2016\/02\/05\/gilman-reagents-organocuprates-what-theyre-used-for\/","title":{"rendered":"Gilman Reagents (Organocuprates): What They&#8217;re Used For"},"content":{"rendered":"<p><strong>So What Are Gilman Reagents Used For, Anyway?<\/strong><\/p>\n<p>Last time we talked about <a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/01\/29\/gilman-reagents-organocuprates-how-theyre-made\/\"><strong>how to make Gilman reagents (organocuprates)<\/strong><\/a>. In this post, we&#8217;ll talk about what they&#8217;re actually used for.<\/p>\n<p>Gilman reagents have some useful contrasts to Grignard reagents.<\/p>\n<ul>\n<li>First of all, they can be used to perform\u00a0<strong>conjugate addition <\/strong>reactions (&#8220;1,4-addition&#8221;) on alpha,-beta unsaturated ketones. In contrast, Grignard reagents tend to only add to the carbonyl carbon.<\/li>\n<li>Secondly, Gilman reagents are useful nucleophiles for SN2 reactions, forming C-C bonds with primary alkyl halides and sulfonates (e.g. tosylates, mesylates)<\/li>\n<li>Third, Gilman reagents will convert acid halides to ketones through nucleophilic acyl substitution. Grignard reagents will add\u00a0<strong>twice<\/strong> to acid halides to give tertiary alcohols.<\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-35162\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/07\/0-Gilman-reagents-are-used-for-conjugate-addition-nucleophilic-substitution-and-conversion-of-acid-halides-to-ketones.gif\" alt=\"Gilman reagents are used for conjugate addition nucleophilic substitution and conversion of acid halides to ketones\" width=\"640\" height=\"704\" \/><\/a><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">Gilman Reagents vs Grignard Reagents<\/a><\/li>\n<li><a href=\"#two\">Conjugate Addition: A Key Reaction of Gilman Reagents<\/a><\/li>\n<li><a href=\"#three\">How do you know whether &#8220;normal&#8221; or &#8220;conjugate&#8221; addition will occur?<\/a><\/li>\n<li><a href=\"#four\">Conjugate Addition Mechanism<\/a><\/li>\n<li><a href=\"#five\">Gilman Reagents Are Great Nucleophiles For S<sub>N<\/sub>2 Reactions<\/a><\/li>\n<li><a href=\"#six\">Conclusion: Gilman Reagents<\/a><\/li>\n<li><a href=\"#notes\">Notes<\/a><\/li>\n<li><a href=\"#quizzes\">Quiz Yourself!<\/a><\/li>\n<li><a href=\"#references\">(Advanced) References and Further Reading<\/a><\/li>\n<\/ol>\n<hr \/>\n<h2><a id=\"one\"><\/a>1. Gilman Reagents vs. Grignard Reagents<\/h2>\n<p>As I hinted at last time, Gilman reagents provide an interesting contrast with Grignard and organolithium reagents.<\/p>\n<p>Remember all those examples of Grignard reagents adding to aldehydes, ketones, and esters? Well, Gilman reagents don&#8217;t generally do that <em>(<span style=\"color: #993366;\">they will add to acid chlorides, but I digress<\/span>)<\/em><\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15386\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-grignard-reagents-add-to-carbonyls-but-gilman-reagents-organocuprates-do-not.gif\" alt=\"grignard reagents add to carbonyls but gilman reagents organocuprates do not\" width=\"600\" height=\"301\" \/><\/p>\n<p>You might find yourself wondering, &#8220;So what?&#8221;. \u00a0Why do we have to bother learning about these things if they&#8217;re not even very reactive?<\/p>\n<p>Well, dear reader, let me fill you in on a second example. We&#8217;ll change one small thing, and everything changes.<\/p>\n<p>Let&#8217;s put a double bond next to the ketone and run the reaction again.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15387\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/2-gilman-reagents-do-conjugate-addition-to-alpha-beta-unsaturated-ketones-and-do-not-add-to-carbonyl.gif\" alt=\"gilman reagents do conjugate addition to alpha beta unsaturated ketones and do not add to carbonyl\" width=\"600\" height=\"412\" \/><\/p>\n<p>Whoa. What just happened there?<\/p>\n<h2><a id=\"two\"><\/a>2. Conjugate Addition: A Key Reaction of Gilman Reagents<\/h2>\n<p>The Grignard reagent reacted the same way (to the carbonyl) but for the organocuprate, see that we&#8217;ve <strong>broken the C-C \u00a0\u03c0 bond (double bond) and formed a new C-C bond ?<\/strong><\/p>\n<p>If that seems strange to you, it should! Isolated alkenes, such as cyclohexene, for instance, don&#8217;t do this reaction.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15388\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/3-gilman-reagents-do-not-react-with-ordinary-alkenes-no-reaction.gif\" alt=\"gilman reagents do not react with ordinary alkenes no reaction\" width=\"600\" height=\"122\" \/><\/p>\n<p><strong>So there must be something important about the fact that the alkene is next to a carbonyl.<\/strong> Why might that be important?<\/p>\n<p>Look at the resonance forms and you will see a clue.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15389\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-why-do-gilman-reagents-organocuprates-attack-alpha-beta-unsaturated-ketones-and-aldehydes.gif\" alt=\"why do gilman reagents organocuprates attack alpha beta unsaturated ketones and aldehydes\" width=\"600\" height=\"309\" \/><\/p>\n<p>There is an important resonance form where the carbon\u00a0<strong>two carbons away<\/strong> from the carbonyl carbon (we call this the &#8220;beta&#8221; (\u03b2) position) bears a positive charge. In the resonance hybrid, therefore, <strong>that carbon bears some partial positive charge.<\/strong><\/p>\n<p>In other words, that carbon is\u00a0<em>electrophilic<\/em>. It can react with nucleophiles! (Such as organocuprates).<\/p>\n<p>Contrast that with ordinary alkenes, where the resonance form with a carbon bearing a negative charge is not an important resonance form. The fact that the charge is placed on <span style=\"text-decoration: underline;\">oxygen<\/span> in the resonance form of an \u03b1,\u03b2 unsaturated system is the key to the relative importance of that resonance form. <em>[<span style=\"color: #993366;\">Compare the basicity of alkoxides (RO-) and alkyllithiums (R-) and that will give you an idea of their relative stabilities<\/span>].<\/em><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15390\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-an-ordinary-alkene-does-not-have-significant-charged-resonance-forms-that-would-make-it-elecrophilic.gif\" alt=\"an ordinary alkene does not have significant charged resonance forms that would make it elecrophilic\" width=\"600\" height=\"122\" \/><\/p>\n<p>[<span style=\"color: #993366;\"><em>For more, see article &#8211; <a href=\"https:\/\/www.masterorganicchemistry.com\/2023\/05\/24\/michael-addition-reaction-conjugate-addition\/\">The Michael Addition and Conjugate Addition<\/a><\/em><\/span>]<\/p>\n<h2><a id=\"three\"><\/a>3. Wait: How Do You Know Whether &#8220;Normal&#8221; Addition or &#8220;Conjugate&#8221; Addition Will Occur?<\/h2>\n<p>This brings up an important question:\u00a0<strong>How do you know whether a nucleophile will attack at the carbonyl carbon\u00a0<\/strong>(sometimes called &#8220;1,2 addition&#8221; in our jargon)\u00a0<strong>or at the beta position\u00a0<\/strong>(&#8220;1,4 addition&#8221; or &#8220;conjugate addition&#8221;).<\/p>\n<p>Simple question. Very difficult to answer succinctly, and too big a topic for this post.<\/p>\n<p>Short answer:\u00a0<strong>memorize<\/strong> that <strong>Grignards add to carbonyls<\/strong>, while <strong>organocuprates do conjugate addition<\/strong>.<\/p>\n<p>(ducks while people throw things at the screen)<\/p>\n<p>I only say &#8220;memorize&#8221; because in order to adequately understand this phenomenon, we&#8217;d have to go into some molecular orbital theory to get at the key concept of &#8220;<a href=\"https:\/\/en.wikipedia.org\/wiki\/HSAB_theory\">Hard Soft Acid Base (HSAB) Theory<\/a>&#8220;, and at this point, we&#8217;re not going to cover it.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15391\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-what-factors-determine-whether-a-nucleophile-will-attack-carbonyl-carbon-or-do-conjugate-addition-hard-nucleophiles-and-soft-nucleophiles-hard-soft-acid-base-theory.gif\" alt=\"what factors determine whether a nucleophile will attack carbonyl carbon or do conjugate addition hard nucleophiles and soft nucleophiles hard soft acid base theory\" width=\"600\" height=\"403\" \/><\/p>\n<p>What about the mechanism of the reaction? Now\u00a0<em>that&#8217;s\u00a0<\/em>something we can cover.<\/p>\n<h2><a id=\"four\"><\/a>4. Conjugate Addition Mechanism<\/h2>\n<p>In the first step, the nucleophile (<em><span style=\"color: #993366;\">which is the<\/span> <strong>pair of electrons in the Cu-CH<sub>3\u00a0<\/sub>bond<\/strong>,\u00a0<strong>NOT<\/strong> the negative charge on copper!<\/em>) forms a bond with the beta position of the ketone. \u00a0The C-C\u00a0\u03c0 bond breaks, forming a negative charge on the alpha carbon. \u00a0We can actually go further and draw a resonance form where we form a new C-C\u00a0\u03c0 bond and place the negative charge on oxygen. You&#8217;ll see this chemical species a\u00a0<strong>lot<\/strong> in subsequent chapters &#8211; it&#8217;s called an\u00a0<b>enolate,\u00a0<\/b>and it&#8217;s very important. (<em>See article: <a href=\"https:\/\/www.masterorganicchemistry.com\/2022\/08\/16\/enolates-properties-reactions\/\">Enolates<\/a><\/em>)<\/p>\n<p>For now, the key takeaway is that the negative charge is on the\u00a0<strong>oxygen<\/strong>, which is considerably more stable (less basic) than having a negative charge on carbon.<\/p>\n<p>Adding acid will protonate the enolate (which is a base, after all) and result in our final product.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15392\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/7-mechanism-of-addition-of-gilman-reagents-organocuprates-to-alpha-beta-unsaturated-ketones-conjugate-addition.gif\" alt=\"mechanism of addition of gilman reagents organocuprates to alpha beta unsaturated ketones conjugate addition\" width=\"630\" height=\"210\" \/><\/p>\n<h2><a id=\"five\"><\/a>5. Gilman Reagents Are Excellent Nucleophiles For S<sub>N<\/sub>2 Reactions<\/h2>\n<p>But wait! Conjugate additions aren&#8217;t all organocuprates can do.<\/p>\n<p>If you have a keen eye for the other posts in this series, you might have noticed that S<sub><em>N<\/em><\/sub>2 reactions were conspicuously absent on the list of reactions that Grignards are useful for. <em>[<span style=\"color: #993366;\">Why&#8217;s that? Great question. The short answer is, we observe that a lot of side reactions tend to occur, like deprotonation and reduction. Using a Grignard reagent to do an S<sub>N<\/sub>2 reaction to form a C-C bond is generally not a great process<\/span>].\u00a0<\/em><\/p>\n<p>However, once we switch to a Gilman reagent, the S<sub>N<\/sub>2 works well. This is a handy reaction to have in the toolbox for forming C-C bonds.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15393\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-contrast-between-gilman-reagents-and-grignard-reagents-is-that-grignard-reagents-do-not-do-sn2-whereas-gilman-reagents-do-sn2.gif\" alt=\"contrast between gilman reagents and grignard reagents is that grignard reagents do not do sn2 whereas gilman reagents do sn2\" width=\"600\" height=\"315\" \/><\/p>\n<p>That about sums it up for Gilman reagents right now. We could add that they can be used to make <strong><a href=\"https:\/\/www.masterorganicchemistry.com\/reaction-guide\/addition-of-organocuprates-gilman-reagents-to-acid-chlorides-to-give-ketones\/\">ketones from acid halides<\/a>\u00a0<\/strong>, I hesitate to put that in at the moment, given that this post is long enough as it is. [<span style=\"color: #993366;\"><em>The general mechanism is covered in this article on <a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/05\/06\/nucleophilic-acyl-substitution\/\">Nucleophilic Acyl Substitution<\/a>.<\/em> <\/span>]<\/p>\n<h2><a id=\"six\"><\/a>6. Conclusion: Gilman Reagents<\/h2>\n<p>Gilman reagents (organocuprates) perform two reactions that Grignard reagents (and organolithiums) do not:<\/p>\n<p>\u2022 They perform conjugate additions to \u03b1,\u03b2 unsaturated ketones.<br \/>\n\u2022 They are effective nucleophiles for S<sub>N<\/sub>2 reactions.<\/p>\n<p>In the next post, we&#8217;ll change to a more controversial topic &#8211; transition metal catalyzed reactions.<\/p>\n<p><strong>Next Post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/03\/10\/the-heck-suzuki-and-olefin-metathesis-reactions\/\">Heck, Suzuki, and Olefin Metathesis Reactions<\/a><\/strong><\/p>\n<hr \/>\n<h2><strong><a id=\"notes\"><\/a>Notes<\/strong><\/h2>\n<div class=\"related-articles\"><p><strong>Related Articles<\/strong><\/p><ul><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2023\/05\/24\/michael-addition-reaction-conjugate-addition\/\" class=\"\"><span>The Michael Addition Reaction and Conjugate Addition<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/03\/10\/the-heck-suzuki-and-olefin-metathesis-reactions\/\" class=\"\"><span>The Heck, Suzuki, and Olefin Metathesis Reactions (And Why They Don\u2019t Belong In Most Introductory Organic Chemistry Courses)<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/reaction-guide\/14-addition-of-organocuprates-gilman-reagents-to-enones\/\" class=\"\"><span>1,4-addition of organocuprates (Gilman reagents) to enones<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/10\/28\/whats-an-organometallic\/\" class=\"\"><span>SN2 reaction of organocuprates (Gilman reagents) with alkyl halides to give alkanes (MOC Membership)<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/01\/29\/gilman-reagents-organocuprates-how-theyre-made\/\" class=\"\"><span>Organocuprates (Gilman Reagents): How They\u2019re Made<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2022\/08\/16\/enolates-properties-reactions\/\" class=\"\"><span>Enolates \u2013 Formation, Stability, and Simple Reactions<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/12\/19\/exploring-resonance-pi-acceptors\/\" class=\"\"><span>Exploring Resonance: Pi-acceptors<\/span><\/a><\/li><\/ul><\/div>\n<p><strong><a id=\"noteone\"><\/a>Note 1. Yet More Information, Because This Hasn&#8217;t Been A Long Enough Blog Post Already<\/strong><\/p>\n<p>Here&#8217;s a quiz for you.\u00a0\u00a0What would be the better nucleophile? An organocopper reagent or an organocuprate reagent?<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15394\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-what-is-better-nucleophile-organocopper-or-organocuprate.gif\" alt=\"what is better nucleophile organocopper or organocuprate\" width=\"600\" height=\"187\" \/><\/p>\n<p>When thinking about this, analyze the leaving group. Therein lies the clue.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15395\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F2-what-makes-gilman-reagent-organocuprate-better-nucleophile-is-that-it-has-better-leaving-group-neutral-versus-cationic.gif\" alt=\"what makes gilman reagent organocuprate better nucleophile is that it has better leaving group neutral versus cationic\" width=\"600\" height=\"449\" \/><\/p>\n<p>When\u00a0<strong>organocopper<\/strong> reagents act as nucleophiles, they go from neutral, relatively stable compounds to ionic Cu+. Although this is a sweeping generalization, charge minimization is generally associated with greater stability in organic chemistry. We&#8217;re going from a neutral compound (organocopper) to a charged ion (Cu+). [<span style=\"color: #993366;\"><em>I could also add that Cu+, being a soft ion, is not very effective in binding to O-, but that&#8217;s a pretty advanced point<\/em><\/span>].<\/p>\n<p>Compare that to\u00a0<strong>organocuprates.\u00a0<\/strong>There, we&#8217;re starting as a relatively unstable\u00a0<strong>charged<\/strong> species, and our final copper product is the <strong>neutral<\/strong> organocopper reagent. This is definitely downhill in terms of stability. It&#8217;s reasonable to expect that the organocuprate will be more reactive, and hence be a better nucleophile.<\/p>\n<p>The same principle can be used to explain why NaBH<sub>4<\/sub> is a better reducing agent than BH<sub>3<\/sub>, and LiAlH<sub>4<\/sub> is a better reducing agent than AlH<sub>3<\/sub>.<\/p>\n<hr \/>\n<h2><a id=\"quizzes\"><\/a>Quiz Yourself!<\/h2>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3085-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <br \/>\n<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3086-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <br \/>\n<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3087-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <br \/>\n<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3088-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <br \/>\n<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3089-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n<hr \/>\n<h2><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/h2>\n<p>Gilman reagents, or Lithium organocuprates (R<sub>2<\/sub>CuLi), are useful nucleophiles in organic synthesis. These have a different reactivity from Grignard reagents and organolithiums, since Gilman reagents are softer.<\/p>\n<p>Gilman reagent formation:<\/p>\n<ol>\n<li><strong>The Preparation of Methylcopper and some Observations on the Decomposition of Organocopper Compounds<br \/>\n<\/strong>Henry Gilman, Reuben G. Jones, and L. A. Woods<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1952<\/strong> <em>17<\/em> (12), 1630-1634<br \/>\n<strong>DOI:<\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo50012a009\">1021\/jo50012a009<\/a><br \/>\nOne of the first papers by Prof. Henry Gilman (U. of Iowa) on \u2018Gilman Reagents\u2019 \u2013 diorganocopper compounds. In this case he describes the preparation of dimethylcopper.<br \/>\n<strong><br \/>\n<\/strong>Conjugate addition of Gilman reagents:<\/li>\n<li><strong>Chemistry of carbanions. XVII. Addition of methyl organometallic reagents to cyclohexenone derivatives<br \/>\n<\/strong>Herbert O. House and William F. Fischer Jr.<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1968<\/strong> <em>33<\/em> (3), 949-956<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo01267a004\">1021\/jo01267a004<\/a><\/li>\n<li><strong>Conjugate Addition Reactions of Organocopper Reagents<\/strong><br \/>\nGary H. Posner<br \/>\n<em> React.<\/em> <strong>1972<\/strong>, <em>19<\/em>, 1-114<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/abs\/10.1002\/0471264180.or019.01\">10.1002\/0471264180.or019.01<\/a><br \/>\n<em>Organic Reactions<\/em> is a series of reviews maintained by the ACS Division of Organic Chemistry, and this review by Prof. Posner, a specialist in cuprate chemistry, covers everything you\u2019d want to know about conjugate additions with copper, as of 1972. Detailed experimental procedures are given towards the end.Ketones can be synthesized by the addition of Gilman reagents to acyl halides:<\/li>\n<li><strong>Methyl and -alkyl ketones from carboxylic acid chlorides and organocopper reagents<br \/>\n<\/strong>G. H. Posner, C. E. Whitten<strong><br \/>\n<\/strong><em>Tetrahedron. Lett. <\/em><strong>1970, <\/strong><em>11 <\/em>(53), 4647-4650<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/www.sciencedirect.com\/science\/article\/abs\/pii\/S0040403900893983\">10.1016\/S0040-4039(00)89398-3<\/a><br \/>\nOne of the original papers on this reaction. Prof. Posner has done a lot of work studying organocopper chemistry in his career.<\/li>\n<li><strong>Organocopper chemistry. Halo-, cyano-, and carbonyl-substituted ketones from the corresponding acyl chlorides and organocopper reagents<br \/>\n<\/strong>Gary H. Posner, Charles E. Whitten, and Paul McFarland<strong><br \/>\n<\/strong><em>Journal of the American Chemical Society<\/em><strong> 1972, <\/strong><em>94<\/em> (14), 5106-5108<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00769a066\">1021\/ja00769a066<\/a><br \/>\nAn extension of the previous paper, expanding the substrate scope of the reaction.The S<sub>N<\/sub>2 reaction of Gilman reagents with alkyl halides is also known as the Corey-Posner-Whitesides-House reaction:<\/li>\n<li><strong>Selective formation of carbon-carbon bonds between unlike groups using organocopper reagents<br \/>\n<\/strong>Elias J. Corey and Gary H. Posner<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1967,<\/strong> <em>89<\/em> (15), 3911-3912<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00991a049\">1021\/ja00991a049<\/a><br \/>\nNobel Laureate Prof. E. J. Corey first describes the reaction of Gilman reagents from CH<sub>3<\/sub>Li ((CH<sub>3<\/sub>)<sub>2<\/sub>CuLi) with alkyl and aryl halides to form new C-C bonds.<\/li>\n<li><strong>Carbon-carbon bond formation by selective coupling of n-alkylcopper reagents with organic halides<br \/>\n<\/strong>Elias J. Corey and Gary H. Posner<strong><br \/>\n<\/strong><em>Journal of the American Chemical Society<\/em> <strong>1968,<\/strong> <em>90<\/em> (20), 5615-5616<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/ja01022a058\">1021\/ja01022a058<\/a><br \/>\nProf. Corey extends this method to <em>n-<\/em>butyl and ethyl (from <em>n-<\/em>BuLi and EtLi) as well.<\/li>\n<li><strong>Reaction of lithium dialkyl- and diarylcuprates with organic halides<br \/>\n<\/strong>George M. Whitesides, William F. Fischer Jr., Joseph San Filippo Jr., Robert W. Bashe, and Herbert O. House<strong><br \/>\n<\/strong><em>Journal of the American Chemical Society<\/em> <strong>1969<\/strong>, <em>91<\/em> (17), 4871-4882<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/ja01045a049\">1021\/ja01045a049<\/a><br \/>\nClassic paper by Prof. G. M. Whitesides (MIT, now Harvard) on the coupling of Gilman reagents (R<sub>2<\/sub>CuLi) with aryl iodides. This reaction is exhaustively studied, and features a thorough mechanistic investigation, which is why his name is included in the reaction.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>So What Are Gilman Reagents Used For, Anyway? Last time we talked about how to make Gilman reagents (organocuprates). In this post, we&#8217;ll talk about <\/p>\n","protected":false},"author":1,"featured_media":35162,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1102],"tags":[364,365,366,1092,1096,1093,1081,1091,215,1095,1094,1090],"post_folder":[],"class_list":["post-9658","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-organometallics","tag-364","tag-2-addition","tag-4-addition","tag-conjugate-addition","tag-elongates","tag-enones","tag-gilman","tag-gilman-reagents","tag-grignards","tag-hard-soft-acids-bases","tag-hsab","tag-organocuprates"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Gilman Reagents (Organocuprates): What They&#039;re Used For<\/title>\n<meta name=\"description\" content=\"Gilman reagents, otherwise known as organocuprates, are useful nucleophiles for conjugate addition as well as SN2 reactions. 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